Substrate processing method and substrate processing apparatus

ABSTRACT

The substrate processing method includes a hydrophilization step of hydrophilizing a surface of a substrate, a processing liquid supplying step of supplying a processing liquid to the hydrophilized surface of the substrate, a processing film forming step in which the processing liquid supplied to the surface of the substrate is solidified or cured to form a processing film on the surface of the substrate, and a peeling step in which a peeling liquid is supplied to the surface of the substrate to peel the processing film from the surface of the substrate. The peeling step includes a penetrating hole forming step in which the processing film is partially dissolved in the peeling liquid to form a penetrating hole in the processing film.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application corresponds to Japanese Patent Application No.2020-53310 filed on Mar. 24, 2020 and Japanese Patent Application No.2020-53309 filed on Mar. 24, 2020 with the Japan Patent Office, theentire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a substrate processing method and asubstrate processing apparatus for processing substrates. Examples ofsubstrates to be processed include substrates such as semiconductorwafers, substrates for optical discs, substrates for magnetic discs,substrates for magneto-optical discs, substrates for photomasks, ceramicsubstrates, substrates for solar cells, and substrates for FPDs (FlatPanel Displays) such as liquid crystal display devices, plasma displaysand organic EL (Electroluminescence) display devices, etc.

2. Description of the Related Art

In a manufacturing process of semiconductor devices, a step is executedin order to remove various types of contaminants adhered to a substrate,residue of a processing liquid or a resist, etc., used in a prior step,and various particles etc. (they may hereinafter be collectivelyreferred to as “removal object.”)

Specifically, it is general that deionized water (DIW), etc., issupplied to a substrate to remove a removal object by physical action ofDIW, or that a chemical liquid which chemically reacts with the removalobject is supplied to the substrate to chemically remove the removalobject.

However, the pattern, having protrusions and recesses, formed on asubstrate becomes finer and more complicated. Therefore, it is becomingmore difficult to remove a removal object by using DIW or a chemicalliquid, while suppressing damage to the pattern.

Thus, a method has been proposed in which a processing liquid issupplied to a surface of a substrate to solidify the processing liquidon the substrate, thereby forming a holding layer which holds a removalobject present on the substrate, thereafter, a peeling liquid issupplied to an upper surface of the substrate, and the holding layer ispeeled and removed from the surface of the substrate together with theremoval object (refer to US Patent Application Publication No.2019/091737).

SUMMARY OF THE INVENTION

In US Patent Application Publication No. 2019/091737, a peeling liquidentry path is formed by a peeling liquid, and the peeling liquid therebyenters a holding layer. However, there is a possibility that, dependingon the condition of the surface of the substrate, the peeling liquid maynot sufficiently enter an interface between the substrate and theholding layer, by which the peeling of the holding layer from thesurface of the substrate is insufficient.

Therefore, there is a demand for a method for effectively peeling from asubstrate a holding layer in a state of holding a removal object. Thus,one object of the present invention is to provide a substrate processingmethod and a substrate processing apparatus capable of effectivelypeeling from a surface of a substrate a processing film in a state ofholding a removal object.

A preferred embodiment of the present invention provides a substrateprocessing method that includes a hydrophilization step ofhydrophilizing a surface of a substrate, a processing liquid supplyingstep of supplying a processing liquid to the hydrophilized surface ofthe substrate, a processing film forming step in which the processingliquid supplied to the surface of the substrate is solidified or curedto form, on the surface of the substrate, a processing film which holdsa removal object present on the surface of the substrate, and a peelingstep in which a peeling liquid is supplied to the surface of thesubstrate, thereby peeling the processing film in a state of holding theremoval object from the surface of the substrate. Therefore, the peelingstep includes a penetrating hole forming step in which the processingfilm is partially dissolved in the peeling liquid to form a penetratinghole in the processing film.

The present inventors have found that, depending on the condition of asurface of a substrate, peeling action by which a peeling liquid peels aprocessing film from the substrate changes. Specifically, the higher thehydrophilicity of the surface of the substrate, the easier it is for theprocessing film to be peeled off by the peeling liquid. Morespecifically, the higher the hydrophilicity of the surface of thesubstrate, the easier it is for the peeling liquid to act on aninterface between the processing film and the substrate, thus making itpossible to effectively peel the processing film from the surface of thesubstrate.

Thus, if a method, in which a processing film is formed on a surface ofa hydrophilized substrate to supply a peeling liquid toward the surfaceof the substrate on which the processing film is formed, is used, theprocessing film can be effectively peeled from the substrate.

Further, a penetrating hole is formed in the processing film by thepeeling liquid supplied toward the surface of the substrate, by whichthe peeling liquid can reach the interface between the processing filmand the substrate via the penetrating hole. Thereby, the peeling liquidacts on an interface between a portion of the processing film whichsurrounds the penetrating hole and the substrate. Therefore, incomparison to a method in which, with no penetrating hole formed in aprocessing film, through infiltration of a peeling liquid into theprocessing film, the peeling liquid reaches an interface between theprocessing film and the substrate, the peeling liquid can act quickly onthe interface between the processing film and the substrate. Althoughthe processing film is partially dissolved by the peeling liquid due toformation of the penetrating hole, a remaining portion thereof is keptin a solid state. Therefore, it is possible to effectively peel theprocessing film in a state of holding a removal object from the surfaceof the substrate.

In this way, while the peeling liquid acts quickly on the interfacebetween the processing film and the substrate, a large portion of theprocessing film can be kept in a solid state. Therefore, it is possibleto effectively peel the processing film from the substrate in a state ofholding a removal object.

In a preferred embodiment of the present invention, the peeling stepincludes a peeling liquid entry step in which the peeling liquid entersbetween the surface of the substrate and the processing film.

The present inventors have found that the higher the hydrophilicity of asurface of a substrate, the higher the wettability (affinity) of apeeling liquid for the substrate, and the easier it is for the peelingliquid to enter between the substrate and the processing film. Thus, bya method in which a processing film is formed on a surface of ahydrophilized substrate to supply a peeling liquid toward the surface ofthe substrate in which the processing film is formed, the peeling liquideffectively enters between the substrate and the processing film.Thereby, it is possible to effectively peel the processing film from thesurface of the substrate.

In a preferred embodiment of the present invention, the hydrophilizationstep includes a step in which a hydrophilizing liquid is supplied to thesurface of the substrate to hydrophilize the surface of the substrate.The hydrophilizing liquid is supplied to the surface of the substrate,by which the hydrophilizing liquid spreads on the surface of thesubstrate, thus enabling the hydrophilizing liquid to spread over anentire surface of the substrate. Therefore, it is possible to uniformlyhydrophilize the entire surface of the substrate. Since the entiresurface of the substrate is hydrophilized, in a subsequent peeling step,the peeling liquid easily acts on the interface between the processingfilm and the substrate on the entire surface of the substrate.Therefore, it is possible to reduce uneven peeling of the processingfilm on the surface of the substrate.

In a preferred embodiment of the present invention, the hydrophilizingliquid is an oxidizing liquid or an organic solvent. Where these liquidsare used as the hydrophilizing liquid, a hydrophobic organic substancepresent on the surface of the substrate is removed, thus making itpossible to hydrophilize the surface of the substrate. Where an organicsolvent is used as the hydrophilizing liquid, a hydrophobic organicsubstance present on the surface of the substrate is dissolved in theorganic solvent to hydrophilize the surface of the substrate.

On the other hand, where an oxidizing liquid is used as thehydrophilizing liquid, a portion of the substrate near the surfacethereof is oxidized. The portion of the substrate near the surfacethereof is oxidized to improve the hydrophilicity of the surface of thesubstrate.

Where an oxidizing liquid is used as the hydrophilizing liquid, thesurface of the substrate can be hydrophilized, regardless of whether anorganic substance is present. In other words, even where an organicsubstance which is less likely to be dissolved by an organic solvent ispresent on the surface of the substrate, the surface of the substratecan be hydrophilized. Therefore, where an oxidizing liquid is used asthe hydrophilizing liquid, it is possible to further enhance thehydrophilicity of the surface of the substrate.

In a preferred embodiment of the present invention, at least any one ofSi, SiN, SiO₂, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru and amorphous carbonis exposed from the surface of the substrate. If these substances areexposed from the surface of the substrate, the surface of the substratecan be hydrophilized by the hydrophilization step.

In a preferred embodiment of the present invention, a surface layer ofthe substrate includes a TiN layer which is exposed from a surface of asubstrate, and the hydrophilizing liquid is an oxidizing liquid. Theoxidizing liquid such as hydrofluoric acid (HF, DHF) or ammonia hydrogenperoxide mixture (APM) is supplied as the hydrophilizing liquid to thesurface of the substrate, by which an oxide film can be formed on thesurface of the TiN layer. APM is also called SC1 (Standard Clean 1). Theoxide film is formed on the surface of the TiN layer, by which thesurface of the substrate can be hydrophilized.

In a preferred embodiment of the present invention, the hydrophilizationstep includes a contact angle reducing step in which the contact angleis reduced such that a contact angle of pure water for the surface ofthe substrate is smaller than 41.7°. The higher the hydrophilicity ofthe surface of the substrate, the smaller the contact angle of purewater for the surface of the substrate becomes. The present inventorshave found that, where the contact angle of pure water for the surfaceof the substrate is smaller than 41.7°, a peeling liquid sufficientlyacts on the interface between the substrate and the processing film.

Then, the surface of the substrate is hydrophilized to reduce thecontact angle such that the contact angle of pure water for the surfaceof the substrate is smaller than 41.7°, thus enabling the peeling liquidto sufficiently act on the interface between the substrate and theprocessing film. Thereby, the processing film in a state of holding aremoval object can be effectively peeled from the substrate.

In a preferred embodiment of the present invention, a contact angle ofpure water for the processing film is larger than 52° and smaller than61°. The present inventors have found that, where the contact angle ofpure water for the processing film is larger than 52° and smaller than61°, the peeling liquid sufficiently acts on the interface between thesubstrate and the processing film.

Thus, where the contact angle of pure water for the processing film islarger than 52° and smaller than 61°, the peeling liquid sufficientlyacts on the interface between the substrate and processing film, thusmaking it possible to effectively peel the processing film.

In a preferred embodiment of the present invention, the processingliquid contains a solvent and a solute. The solute has a high solubilitycomponent and a low solubility component which is lower in solubility inthe peeling liquid than the high solubility component. The processingfilm forming step includes a step which forms the processing film havinga high solubility solid formed by the high solubility component and alow solubility solid formed by the low solubility component. Then, inthe peeling step, the high solubility solid is dissolved in the peelingliquid to peel the processing film in a state of holding the removalobject from the surface of the substrate.

According to the above-described method, the solubility of the highsolubility component in the peeling liquid is higher than that of thelow solubility component in the peeling liquid. Therefore, the highsolubility solid formed by the high solubility component is more easilydissolved in the peeling liquid than the low solubility solid formed bythe low solubility component.

Therefore, the peeling liquid is supplied to the surface of thesubstrate to dissolve the high solubility solid in the peeling liquid,by which a space is formed in the processing film. On the other hand,the low solubility solid is not dissolved in the peeling liquid but keptin a solid state.

Therefore, while the high solubility solid is dissolved in the peelingliquid, the low solubility solid is not dissolved in the peeling liquidbut can be kept in a solid state. Accordingly, the peeling liquid passesthrough the space (gap, path) formed by dissolution of the highsolubility solid and reaches an interface between the substrate and thelow solubility solid.

Therefore, while a removal object is held by the low solubility solid,the peeling liquid acts on the interface between the low solubilitysolid and the substrate. As a result, while the processing film isquickly peeled from the substrate, the removal object can be removedefficiently from the substrate together with the processing film.

A preferred embodiment of the present invention provides a substrateprocessing method that includes a hydrophilization step ofhydrophilizing a surface of a substrate, a processing liquid supplyingstep of supplying a processing liquid to the hydrophilized surface ofthe substrate, a processing film forming step in which the processingliquid supplied to the surface of the substrate is solidified or curedto form, on the surface of the substrate, a processing film which holdsa removal object present on the surface of the substrate, and a peelingstep in which a peeling liquid is supplied to the surface of thesubstrate to peel the processing film in a state of holding the removalobject from the surface of the substrate, and that the hydrophilizationstep includes a contact angle reducing step in which the contact angleis reduced so that a contact angle of pure water for the surface of thesubstrate is smaller than 41.7°.

According to the above-described method, the processing film is formedon the hydrophilized surface of the substrate, and the peeling liquid issupplied toward the surface of the substrate on which the processingfilm is formed. As described previously, the higher the hydrophilicityof the surface of the substrate, the more easily the peeling liquid actson an interface between the processing film and the substrate, and theprocessing film can be effectively peeled from the surface of thesubstrate. In this method, the surface of the substrate is hydrophilizedso that the contact angle of pure water for the surface of the substrateis smaller than 41.7°. Therefore, the peeling liquid sufficiently actson the interface between the substrate and the processing film. Thereby,it is possible to effectively peel from the substrate the processingfilm in a state of holding a removal object.

In a preferred embodiment of the present invention, the contact angle ofpure water for the processing film is larger than 52° and smaller than61°. Therefore, the peeling liquid sufficiently acts on the interfacebetween the substrate and the processing film, and the processing filmcan be effectively peeled.

A preferred embodiment of the present invention provides a substrateprocessing method that includes a hydrophilization step ofhydrophilizing a surface of a substrate, a processing liquid supplyingstep of supplying a processing liquid to the hydrophilized surface ofthe substrate, a processing film forming step in which the processingliquid supplied to the surface of the substrate is solidified or curedto form, on the surface of the substrate, a processing film which holdsa removal object present on the surface of the substrate, and a peelingstep in which a peeling liquid is supplied to the surface of thesubstrate to peel, from the surface of the substrate, the processingfilm in a state of holding the removal object, and that the processingliquid contains a solvent and a solute, and the solute has a highsolubility component and a low solubility component lower in solubilityin the peeling liquid than the high solubility component. In thesubstrate processing method, the processing film forming step includes astep which forms the processing film having a high solubility solidformed by the high solubility component and a low solubility solidformed by the low solubility component. Then, in the peeling step, thehigh solubility solid is dissolved in the peeling liquid to peel theprocessing film in a state of holding the removal object from thesurface of the substrate.

According to the above-described method, the processing film is formedon the hydrophilized surface of the substrate, and the peeling liquid issupplied toward the surface of the substrate on which the processingfilm is formed. As described previously, the higher the hydrophilicityof the surface of the substrate is, the more easily the peeling liquidacts on the interface between the processing film and the substrate, andthe processing film can be effectively peeled from the surface of thesubstrate. Therefore, it is possible to effectively peel the processingfilm from the substrate.

According to the above-described method, the solubility of the highsolubility component in the peeling liquid is higher than that of thelow solubility component in the peeling liquid. Therefore, the highsolubility solid formed by the high solubility component is more easilydissolved in the peeling liquid than the low solubility solid formed bythe low solubility component.

Therefore, the peeling liquid is supplied to the surface of thesubstrate to dissolve the high solubility solid in the peeling liquid,thereby forming a space in the processing film. On the other hand, thelow solubility solid is not dissolved in the peeling liquid but kept ina solid state.

Therefore, while the high solubility solid is dissolved in the peelingliquid, the low solubility solid is not dissolved in the peeling liquidbut can be kept in a solid state. Accordingly, the peeling liquid passesthrough the space (gap, path) formed by dissolution of the highsolubility solid and can reach an interface between the substrate andthe low solubility solid.

Therefore, while a removal object is held by the low solubility solid,the peeling liquid acts on the interface between the low solubilitysolid and the substrate. Thereby, it is possible to effectively peelfrom the substrate the processing film in a state of holding the removalobject.

As a result, while the processing film is quickly peeled from thesubstrate, the removal object can be removed efficiently from thesubstrate together with the processing film.

In this substrate processing method, at least any one of Si, SiN, SiO₂,SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru and amorphous carbon is exposed fromthe surface of the substrate. Where these substances are exposed fromthe surface of the substrate, the surface of the substrate can behydrophilized by the hydrophilization step.

In this substrate processing method, the hydrophilization step includesthe contact angle reducing step in which the contact angle is reducedsuch that a contact angle of pure water for the surface of the substrateis smaller than 41.7°. Therefore, the peeling liquid sufficiently actson an interface between the substrate and the processing film. Thereby,it is possible to effectively peel from the substrate the processingfilm in a state of holding a removal object.

A preferred embodiment of the present invention provides a substrateprocessing apparatus that includes a hydrophilizing liquid supplyingunit which supplies a hydrophilizing liquid, which hydrophilizes asurface of a substrate to the surface of the substrate, a processingliquid supplying unit which supplies a processing liquid to the surfaceof the substrate, a processing film forming unit in which the processingliquid in contact with the surface of the substrate is solidified orcured to form a processing film, a peeling liquid supplying unit whichsupplies a peeling liquid, which peels the processing film formed on thesurface of the substrate, to the surface of the substrate, and acontroller which controls the hydrophilizing liquid supplying unit, theprocessing liquid supplying unit, the processing film forming unit andthe peeling liquid supplying unit.

Then, the controller that is included in the substrate processingapparatus is programmed such that the hydrophilizing liquid is suppliedfrom the hydrophilizing liquid supplying unit to the surface of thesubstrate to hydrophilize the surface of the substrate, the processingliquid is supplied from the processing liquid supplying unit to thehydrophilized surface of the substrate, the processing liquid suppliedto the surface of the substrate is solidified or cured by the processingfilm forming unit to form, on the surface of the substrate, a processingfilm which holds a removal object present on the surface of thesubstrate, a peeling liquid is supplied to the surface of the substratefrom the peeling liquid supplying unit to peel the processing film in astate of holding the removal object from the surface of the substrate,and the processing film is partially dissolved by the peeling liquid toform a penetrating hole on the processing film.

According to the present configuration, the same effects as those of theabove-described substrate processing method are obtained.

A preferred embodiment of the present invention provides a substrateprocessing apparatus that includes a hydrophilizing liquid supplyingunit which supplies a hydrophilizing liquid, which hydrophilizes asurface of a substrate, to the surface of the substrate, a processingliquid supplying unit which supplies a processing liquid to the surfaceof the substrate, a processing film forming unit in which the processingliquid in contact with the surface of the substrate is solidified orcured to form a processing film, a peeling liquid supplying unit whichsupplies a peeling liquid, which peels the processing film formed on thesurface of the substrate, to the surface of the substrate, and acontroller which controls the hydrophilizing liquid supplying unit, theprocessing liquid supplying unit, the processing film forming unit andthe peeling liquid supplying unit, and that the processing liquidcontains a solvent and a solute, the solute has a high solubilitycomponent and a low solubility component lower in solubility in thepeeling liquid than the high solubility component, and the processingfilm has a high solubility solid formed by the high solubility componentand a low solubility solid formed by the low solubility component.

Then, the controller included in the substrate processing apparatus isprogrammed so that the hydrophilizing liquid is supplied from thehydrophilizing liquid supplying unit to the surface of the substrate tohydrophilize the surface of the substrate, the processing liquid issupplied from the processing liquid supplying unit to the hydrophilizedsurface of the substrate, the processing liquid supplied to the surfaceof the substrate is solidified or cured by the processing film formingunit to form, on the surface of the substrate, a processing film whichholds a removal object present on the surface of the substrate, apeeling liquid is supplied from the peeling liquid supplying unit to thesurface of the substrate to dissolve the high solubility solid in thepeeling liquid, thereby peeling the processing film in a state ofholding the removal object from the surface of the substrate.

According to the present configuration, the same effects as those of theabove-described substrate processing method are obtained.

A preferred embodiment of the present invention provides a substrateprocessing method that includes a processing liquid supplying step whichsupplies a processing liquid toward a surface of a substrate, aprocessing film forming step in which the processing liquid supplied tothe surface of the substrate is solidified or cured to form, on thesurface of the substrate, a processing film which holds a removal objectpresent on the surface of the substrate, a peeling removal step in whicha peeling liquid is supplied toward the surface of the substrate, topartially dissolve the processing film in the peeling liquid, to peelthe processing film in a state of holding the removal object from thesurface of the substrate and to remove the peeled processing filmoutside the substrate, and a residue removing step in which, after thepeeling removal step, a residue removing liquid is supplied toward thesurface of the substrate to remove a residue of the processing filmremaining on the surface of the substrate. The peeling liquid is aliquid mixture of an organic solvent and water, and the residue removingliquid is an organic solvent which is composed of the same substance asthe organic solvent contained in the liquid mixture.

According to the above-described method, the processing liquid suppliedto the surface of the substrate is solidified or cured to form theprocessing film which holds a removal object. Thereafter, the peelingliquid is supplied toward the surface of the substrate. The peelingliquid is supplied to partially dissolve the processing film, theprocessing film in a state of holding the removal object is peeled fromthe surface of the substrate, and the processing film which has beenthus peeled is removed outside the substrate.

According to the above-described method, the peeling liquid is a liquidmixture of an organic solvent and water. The processing film is moreeasily dissolved in an organic solvent than in water. Therefore, thepeeling liquid which is a liquid mixture of an organic solvent and wateris less likely to dissolve the processing film than an organic solvent.Therefore, the processing film is partially dissolved by the peelingliquid to form a space (gap, path) in the processing film.

The peeling liquid can reach the surface of the substrate through thespace. The peeling liquid which has reached the surface of the substrateacts on an interface between the processing film and the substrate.Therefore, in comparison to a method in which, with no space formed inthe processing film, through infiltration of a peeling liquid into theprocessing film, the peeling liquid reaches the interface between theprocessing film and the substrate, a large amount of the peeling liquidquickly reaches the interface between the processing film and thesubstrate.

The processing film is more easily dissolved in an organic solvent thanin water. Therefore, a liquid mixture of an organic solvent and watereasily dissolves the processing film in comparison to water. Althoughthe processing film is partially dissolved for formation of the space, aremaining portion thereof is kept in a solid state. Therefore, thepeeling liquid appropriately dissolves a surface of the processing film,the portion of which is kept in a solid state. Therefore, the processingfilm in a state of holding a removal object can be effectively peeledfrom the surface of the substrate and removed from the substrate.

The peeling liquid is continuously supplied to remove the processingfilm from the surface of the substrate. There may be a case in which,even after the processing film has been removed from the surface of thesubstrate, a residue of the processing film adheres to the surface ofthe substrate. Even in this case, the residue of the processing film isremoved by the residue removing liquid. Thereby, it is possible tosatisfactorily clean the surface of the substrate.

According to the above-described method, the residue removing liquid isan organic solvent which is composed of the same substance as an organicsolvent contained in a liquid mixture. That is, the organic solvent inthe liquid mixture used as the peeling liquid and the organic solventused as the residue removing liquid are the same organic compound. Incomparison to a method in which the organic solvent in the liquidmixture used as the peeling liquid is a substance different from theorganic solvent used as the residue removing liquid, types of the liquidto be used can be reduced. Therefore, it is possible to reduce costsnecessary for removing a removal object from the substrate.

In a preferred embodiment of the present invention, the peeling removalstep includes a step of forming a penetrating hole in the processingfilm by partially dissolving the processing film in the peeling liquid.

According to the above-described method, the peeling liquid forms thepenetrating hole in the processing film. Therefore, the peeling liquidpasses through the penetrating hole and reaches the surface of thesubstrate. The peeling liquid which has reached the surface of thesubstrate acts on an interface between a portion of the processing filmwhich surrounds the penetrating hole and the substrate. Therefore, incomparison to a method in which, with no penetrating hole formed in aprocessing film, through infiltration of a peeling liquid into theprocessing film, the peeling liquid reaches an interface between theprocessing film and the substrate, a large amount of the peeling liquidquickly reaches the interface between the processing film and thesubstrate.

In a preferred embodiment of the present invention, the processingliquid contains a solvent and a solute which is dissolved by thesolvent. The solute has a high solubility component and a low solubilitycomponent which is lower in solubility in the peeling liquid than thehigh solubility component. The processing film forming step includes astep which forms the processing film having a high solubility solidformed by the high solubility component and a low solubility solidformed by the low solubility component. Therefore, the peeling removalstep includes a step in which the high solubility solid is dissolved inthe peeling liquid to peel from the surface of the substrate theprocessing film in a state of holding the removal object.

According to the above-described method, the solubility of the highsolubility component in the peeling liquid is higher than that of thelow solubility component in the peeling liquid. Therefore, the highsolubility solid formed by the high solubility component is more easilydissolved in the peeling liquid than the low solubility solid formed bythe low solubility component. Therefore, the high solubility solid isdissolved by the peeling liquid to form a space in the processing film.On the other hand, the low solubility solid is not dissolved by thepeeling liquid but kept in a solid state.

Therefore, while the high solubility solid is dissolved in the peelingliquid, the low solubility solid is not dissolved in the peeling liquidbut can be kept in a solid state. Accordingly, the peeling liquid passesthrough the space formed by dissolution of the high solubility solid andreaches an interface between the substrate and the low solubility solid.

As a result, while a removal object is held by the low solubility solid,the peeling liquid acts on the interface between the low solubilitysolid and the substrate. Thereby, while the processing film is quicklypeeled from the substrate, the removal object can be effectively removedfrom the substrate.

In a preferred embodiment of the present invention, the peeling removalstep includes a peeling liquid entry step in which the peeling liquidenters between the surface of the substrate and the processing film.Therefore, the peeling liquid acts on an interface between theprocessing film and the substrate to more efficiently peel theprocessing film from the surface of the substrate.

In a preferred embodiment of the present invention, the peeling removalstep includes a hydrophilization step which hydrophilizes the surface ofthe substrate by the peeling liquid.

The higher the hydrophilicity of an upper surface of the substrate, themore easily the peeling liquid acts on the interface between thesubstrate and the processing film, and the processing film can beeffectively peeled from the surface of the substrate. Therefore, thesurface of the substrate is hydrophilized by the peeling liquid and,thereby, the processing film can be effectively peeled.

In a preferred embodiment of the present invention, the organic solventis IPA, and a mass percent concentration of IPA in the liquid mixture isnot less than 12% and not more than 33%. Where the mass percentconcentration of IPA in the liquid mixture is not less than 12% and notmore than 33%, the surface of the processing film can be appropriatelydissolved. Therefore, with no removal object detached from theprocessing film, the processing film in a state of holding the removalobject can be peeled from the surface of the substrate.

In a preferred embodiment of the present invention, the substrateprocessing method further includes a prior hydrophilization step inwhich the surface of the substrate is hydrophilized prior to the supplyof the processing liquid to the surface of the substrate.

According to the above-described method, prior to the supply of theprocessing liquid to the surface of the substrate, the surface of thesubstrate is hydrophilized. That is, the surface of the substrate ishydrophilized in advance. Therefore, the processing film is formed onthe hydrophilized surface of the substrate. Accordingly, it is possibleto effectively peel the processing film from the substrate by thepeeling liquid.

A preferred embodiment of the present invention provides a substrateprocessing method that includes a processing liquid supplying step ofsupplying a processing liquid toward a surface of a substrate, aprocessing film forming step in which the processing liquid supplied tothe surface of the substrate is solidified or cured to form, on thesurface of the substrate, a processing film which holds a removal objectpresent on the surface of the substrate, a penetrating hole forming stepin which a dissolving liquid is supplied toward the surface of thesubstrate to partially dissolve the processing film in the dissolvingliquid, thereby forming a penetrating hole in the processing film, and apeeling step in which a peeling liquid is supplied toward the surface ofthe substrate and, thereby, the peeling liquid passes through thepenetrating hole to peel the processing film in a state of holding theremoval object from the surface of the substrate.

According to the above-described method, the processing liquid suppliedto the surface of the substrate is solidified or cured to form theprocessing film which holds the removal object. Thereafter, thedissolving liquid is supplied toward the surface of the substrate.Thereby, the processing film is partially dissolved to form thepenetrating hole on the processing film. After that, the peeling liquidis supplied toward the surface of the substrate. Thereby, the peelingliquid passes through the penetrating hole and reaches an interfacebetween the substrate and the peeling liquid, and the processing film ina state of holding the removal object is peeled from the surface of thesubstrate by the peeling liquid.

The penetrating hole is formed on the processing film by the dissolvingliquid and, therefore, the peeling liquid reaches the surface of thesubstrate through the penetrating hole. The peeling liquid which hasreached the surface of the substrate acts on an interface between aportion of the processing film which surrounds the penetrating hole andthe substrate. Therefore, in comparison to a method in which, with nopenetrating hole formed in the processing film, the peeling liquidpasses through the processing film and the peeling liquid reaches aninterface between the processing film and the substrate, a large amountof the peeling liquid quickly reaches the interface between theprocessing film and the substrate.

Although the processing film is partially dissolved for formation of thepenetrating hole, a remaining portion thereof is kept in a solid state.Therefore, it is possible to effectively peel the processing film in astate of holding the removal object from the surface of the substrate.

Further, according to the above-described method, the formation of thepenetrating hole and peeling of the processing film are executed byusing different liquids (a dissolving liquid and a peeling liquid).Therefore, the peeling liquid and the dissolving liquid can be selectedfrom liquids suitable for individual roles. That is, a liquid suitablefor partial dissolution of the processing film can be selected as thedissolving liquid, and a liquid suitable for peeling of the processingfilm can be selected as the peeling liquid. Accordingly, it is possibleto suppress dissolution of the processing film by the dissolving liquidand suppress detachment of a removal object from the processing film.Therefore, it is possible to effectively peel the processing film in astate of holding the removal object.

In a preferred embodiment of the present invention, the processingliquid contains a solvent and a solute which is dissolved by thesolvent. The solute has a high solubility component and a low solubilitycomponent lower in solubility in the dissolving liquid than the highsolubility component. The processing film forming step includes a stepwhich forms the processing film which has a high solubility solid formedby the high solubility component and a low solubility solid formed bythe low solubility component. Therefore, the penetrating hole formingstep includes a step in which the high solubility solid is dissolved inthe dissolving liquid to form the penetrating hole on the processingfilm.

According to the above-described method, the solubility of the highsolubility component in the dissolving liquid is higher than that of thelow solubility component in the dissolving liquid. Therefore, the highsolubility solid formed by the high solubility component is more easilydissolved in the dissolving liquid than the low solubility solid formedby the low solubility component. Therefore, the high solubility solid isdissolved by the dissolving liquid to form the penetrating hole on theprocessing film. On the other hand, the low solubility solid is notdissolved in the dissolving liquid but kept in a solid state.

Therefore, while the high solubility solid is dissolved in thedissolving liquid, the low solubility solid can be kept in a solid statewithout being dissolved in the dissolving liquid. Accordingly, thepeeling liquid reaches an interface between the substrate and the lowsolubility solid through the penetrating hole formed by dissolution ofthe high solubility solid.

As a result, while the removal object is held by the low solubilitysolid, the peeling liquid acts on the interface between the lowsolubility solid and the substrate. The processing film is, thereby,quickly peeled from the substrate and the removal object can beeffectively removed from the substrate, together with the processingfilm.

In a preferred embodiment of the present invention, the peeling stepincludes a peeling liquid entry step in which the peeling liquid entersbetween the surface of the substrate and the processing film. Therefore,the peeling liquid acts on an interface between the processing film andthe substrate, and the processing film can be more efficiently peeledfrom the surface of the substrate.

In a preferred embodiment of the present invention, the peeling liquidis a liquid mixture of an organic solvent and water. The processing filmis more easily dissolved in an organic solvent and less likely to bedissolved in water. Where the peeling liquid is a liquid mixture of anorganic solvent and water, with a removal object held, the surface ofthe processing film can be slightly dissolved to such an extent that theprocessing film can be peeled from the surface of the substrate. Forexample, where the organic solvent is IPA and the mass percentconcentration of IPA in the liquid mixture is not less than 12% and notmore than 33%, the surface of the processing film can be appropriatelydissolved. Therefore, the processing film in a state of holding theremoval object can be peeled from the surface of the substrate, with noremoval object detached from the processing film.

In a preferred embodiment of the present invention, the substrateprocessing method further includes a removal step in which, even afterthe peeling of the processing film from substrate, the peeling liquid iscontinuously supplied to the surface of the substrate and the processingfilm which has been peeled from the surface of the substrate is therebyremoved outside the substrate, and a residue removing step in which,after the removal step, a residue removing liquid is supplied toward thesurface of the substrate, thereby removing a residue of the processingfilm remaining on the surface of the substrate. Then, the residueremoving liquid is an organic solvent which is composed of the samesubstance as the organic solvent in the liquid mixture.

According to the above-described method, the peeling liquid iscontinuously supplied to remove the processing film from the surface ofthe substrate. There may be a case in which, even after removal of theprocessing film from the surface of the substrate, a residue of theprocessing film adheres to the surface of the substrate. Even in thiscase, the residue of the processing film can be removed by the residueremoving liquid. Thereby, it is possible to satisfactorily clean thesurface of the substrate.

According to the above-described method, the residue removing liquid isan organic solvent which is composed of the same substance as an organicsolvent in a liquid mixture. That is, the organic solvent in the liquidmixture used as the peeling liquid and the organic solvent used as theresidue removing liquid are the same organic compound. In comparison toa case in which the organic solvent in the liquid mixture used as thepeeling liquid is different from the organic solvent used as the residueremoving liquid, it is possible to reduce types of the liquid to beused. Therefore, it is possible to reduce costs necessary for removingthe removal object from the substrate.

In a preferred embodiment of the present invention, the substrateprocessing method further includes a removal step in which, even afterthe processing film has been peeled from the substrate, the peelingliquid is continuously supplied to the surface of the substrate, therebyremoving the processing film which has been peeled from the surface ofthe substrate outside the substrate and a residue removing step inwhich, after the removal step, a residue removing liquid is supplied tothe surface of the substrate, thereby removing a residue of theprocessing film remaining on the surface of the substrate.

According to the above-described method, the peeling liquid iscontinuously supplied to remove the processing film outside thesubstrate. There may be a case in which, even after removal of theprocessing film from the surface of the substrate, a residue of theprocessing film adheres to the surface of the substrate. Even in thiscase, the residue of the processing film is removed by the residueremoving liquid. Thereby, it is possible to satisfactorily clean thesurface of the substrate.

In a preferred embodiment of the present invention, the peeling stepincludes a hydrophilization step which hydrophilizes the surface of thesubstrate by the peeling liquid.

According to the above-described method, the surface of the substrate ishydrophilized by the peeling liquid. Therefore, a portion of the surfaceof the substrate which is exposed by formation of a penetrating hole ishydrophilized by the peeling liquid and at the same time, the peelingliquid also acts on an interface between a portion of the processingfilm which surrounds the penetrating hole and the substrate.Accordingly, the processing film in a state of holding the removalobject can be effectively peeled from the surface of the substrate.

In a preferred embodiment of the present invention, the substrateprocessing method further includes a hydrophilization step in which,before the peeling step, a hydrophilizing liquid is supplied toward thesurface of the substrate and, thereby, the hydrophilizing liquid passesthrough the penetrating hole to hydrophilize the surface of thesubstrate.

According to the above-described method, the hydrophilizing liquid issupplied toward the surface of the substrate. The hydrophilizing liquidpasses through the penetrating hole and reaches the surface of thesubstrate, thereby hydrophilizing a portion of the surface of thesubstrate which is exposed by formation of the penetrating hole.

The higher the hydrophilicity of the upper surface of the substrate, themore easily the peeling liquid acts on an interface between thesubstrate and the processing film, and the processing film can beeffectively peeled from the surface of the substrate. Therefore, if aportion of the surface of the substrate which is exposed by formation ofthe penetrating hole is hydrophilized before the supply of the peelingliquid toward the surface of the substrate, the peeling liquid acts onan interface between a portion of the processing film which surroundsthe penetrating hole and the substrate, and the processing film canthereby be effectively peeled.

In a preferred embodiment of the present invention, the hydrophilizingliquid is an oxidizing liquid which oxidizes the surface of thesubstrate. Where the oxidizing liquid is used as the hydrophilizingliquid, a portion of the substrate near the surface thereof (surfacelayer) is oxidized. The surface layer of the substrate is oxidized, bywhich oxygen atoms bond to a substance exposed from the surface of thesubstrate. Oxygen atoms bond to the substance exposed from the surfaceof the substrate, thereby hydrophilizing the surface of the substrate.

In a preferred embodiment of the present invention, the dissolvingliquid, the hydrophilizing liquid and the peeling liquid contain asubstance which is different from each other.

In a preferred embodiment of the present invention, the peeling liquidand the dissolving liquid contain a substance which is different fromeach other.

In a preferred embodiment of the present invention, the dissolvingliquid is an alkaline liquid.

In a preferred embodiment of the present invention, the substrateprocessing method further includes a prior hydrophilization step inwhich, prior to the supply of the processing liquid to the surface ofthe substrate, the surface of the substrate is hydrophilized.

According to the above-described method, prior to the supply of theprocessing liquid to the surface of the substrate, that is, the surfaceof the substrate is hydrophilized in advance. The processing film is,therefore, formed on the hydrophilized surface of the substrate.Accordingly, it is possible to effectively peel the processing film fromthe substrate by the peeling liquid.

A preferred embodiment of the present invention provides a substrateprocessing method that includes a processing liquid supplying step ofsupplying a processing liquid toward a surface of a substrate, aprocessing film forming step in which the processing liquid supplied tothe surface of the substrate is solidified or cured to form, on thesurface of the substrate, a processing film which holds a removal objectpresent on the surface of the substrate, a dissolving step in which adissolving liquid is supplied toward the surface of the substrate andthe processing film is partially dissolved in the dissolving liquid, anda peeling step in which, after the dissolving step, a peeling liquid issupplied toward the surface of the substrate and the processing film ina state of holding the removal object is thereby peeled from the surfaceof the substrate by the peeling liquid, and that the processing liquidcontains a solvent and a solute which is dissolved by the solvent, thesolute has a high solubility component and a low solubility componentlower in solubility in the dissolving liquid than the high solubilitycomponent, the processing film forming step includes a step which formsthe processing film having a high solubility solid formed by the highsolubility component and a low solubility solid formed by the lowsolubility component, and the dissolving step includes a step whichdissolves the high solubility solid in the dissolving liquid.

According to the above-described method, the processing liquid suppliedto the surface of the substrate is solidified or cured to form aprocessing film which holds a removal object. After that, the dissolvingliquid is supplied toward the surface of the substrate. Thereby, theprocessing film is partially dissolved to form a space inside theprocessing film. After that, the peeling liquid is supplied to thesurface of the substrate. Thereby, the peeling liquid passes through thespace inside the processing film and reaches an interface between thesubstrate and the peeling liquid. The processing film in a state ofholding the removal object is peeled from the surface of the substrateby the peeling liquid.

The solubility of the high solubility component in the dissolving liquidis higher than that of the low solubility component in the dissolvingliquid. Therefore, the high solubility solid formed by the highsolubility component is more easily dissolved in the dissolving liquidthan the low solubility solid formed by the low solubility component.Accordingly, the high solubility solid is dissolved by the dissolvingliquid to form a space in the processing film. On the other hand, thelow solubility solid is not dissolved in the peeling liquid but kept ina solid state.

Therefore, while the high solubility solid is dissolved in thedissolving liquid, the low solubility solid can be kept in a solid statewithout being dissolved in the dissolving liquid. Accordingly, thepeeling liquid passes through the space formed by dissolution of thehigh solubility solid and reaches an interface between the substrate andthe low solubility solid.

As a result, while a removal object is held by the low solubility solid,the peeling liquid acts on the interface between the low solubilitysolid and the substrate. Thereby, the processing film is quickly peeledfrom the substrate, and the removal object can be effectively removedfrom the substrate, together with the processing film.

Further, according to the above-described method, the dissolution of thehigh solubility solid and the peeling of the processing film are carriedout by different liquids (a dissolving liquid and a peeling liquid).Therefore, each of the peeling liquid and the dissolving liquid can beselected from liquids suitable for individual roles. That is, a liquidsuitable for partial dissolution of the high solubility solid can beselected as the dissolving liquid, and a liquid suitable for the peelingof the processing film can be selected as the peeling liquid.

For example, if a liquid having a larger difference in solubilitybetween the high solubility solid and the low solubility solid than thepeeling liquid is used as the dissolving liquid, it is possible tosuppress loss of the low solubility solid by the dissolving liquid andsuppress detachment of a removal object from the low solubility solid.Therefore, it is possible to effectively peel the processing film in astate of holding the removal object.

A preferred embodiment of the present invention provides a substrateprocessing apparatus that includes a processing liquid supplying unitwhich supplies a processing liquid to a surface of a substrate, aprocessing film forming unit in which the processing liquid in contactwith the surface of the substrate is solidified or cured to form aprocessing film, a peeling liquid supplying unit which supplies apeeling liquid, which peels the processing film formed on the surface ofthe substrate, to the surface of the substrate, a residue removingliquid supplying unit which supplies, a residue removing liquid, whichremoves a residue of the processing film present on the surface of thesubstrate, to the surface of the substrate, and a controller whichcontrols the processing liquid supplying unit, the processing filmforming unit, the peeling liquid supplying unit and the residue removingliquid supplying unit.

Then, the controller is programmed so that a processing liquid issupplied to the substrate from the processing liquid supplying unit, theprocessing liquid supplied toward the surface of the substrate issolidified or cured by the processing film forming unit to form, on thesurface of the substrate, a processing film which holds a removal objectpresent on the surface of the substrate, the peeling liquid is suppliedtoward the substrate from the peeling liquid supplying unit, therebypartially dissolving the processing film in the peeling liquid, theprocessing film in a state of holding the removal object is peeled fromthe surface of the substrate, the peeled processing film is removedoutside the substrate, and a residue removing liquid is supplied towardthe surface of the substrate from the residue removing liquid supplyingunit, thereby removing a residue of the processing film remaining on thesurface of the substrate. Further, the peeling liquid is a liquidmixture of an organic solvent and water, and the residue removing liquidis an organic solvent which is composed of the same substance as theorganic solvent in the liquid mixture.

According to the present apparatus, the same effects as those of theabove-described substrate processing method are obtained.

A preferred embodiment of the present invention provides a substrateprocessing apparatus that includes a processing liquid supplying unitwhich supplies a processing liquid to a surface of a substrate, aprocessing film forming unit in which the processing liquid in contactwith the surface of the substrate is solidified or cured to form aprocessing film, a dissolving liquid supplying unit which supplies adissolving liquid which partially dissolves the processing film formedon the surface of the substrate, to the surface of the substrate, apeeling liquid supplying unit which supplies, to the surface of thesubstrate, a peeling liquid for peeling the processing film formed onthe surface of the substrate, and a controller which controls theprocessing liquid supplying unit, the processing film forming unit, thedissolving liquid supplying unit and the peeling liquid supplying unit.

Then, the controller is programmed so that a processing liquid issupplied to the substrate from the processing liquid supplying unit, theprocessing liquid supplied toward the surface of the substrate issolidified or cured by the processing film forming unit to form, on thesurface of the substrate, a processing film which holds a removal objectpresent on the surface of the substrate, a dissolving liquid is suppliedtoward the substrate from the dissolving liquid supplying unit, therebypartially dissolving the processing film in the dissolving liquid toform a penetrating hole on the processing film, a peeling liquid issupplied toward the substrate from the peeling liquid supplying unit andthe peeling liquid passes through the penetrating hole, by which theprocessing film in a state of holding the removal object is peeled fromthe surface of the substrate.

According to the present apparatus, the same effects as those of theabove-described substrate processing method are obtained.

A preferred embodiment of the present invention provides a substrateprocessing apparatus that includes a processing liquid supplying unitwhich supplies a processing liquid to a surface of a substrate, aprocessing film forming unit in which the processing liquid in contactwith the surface of the substrate is solidified or cured to form aprocessing film, a dissolving liquid supplying unit which supplies adissolving liquid which partially dissolves the processing film formedon the surface of the substrate, to the surface of the substrate, apeeling liquid supplying unit which supplies, to the surface of thesubstrate, a peeling liquid for peeling the processing film formed onthe surface of the substrate, and a controller which controls theprocessing liquid supplying unit, the processing film forming unit, thedissolving liquid supplying unit and the peeling liquid supplying unit,and that the processing liquid contains a solvent and a solute which isdissolved by the solvent, and the solute has a high solubility componentand a low solubility component lower in solubility in the peeling liquidsupplied from the peeling liquid supplying unit than the high solubilitycomponent.

Further, the controller included in the substrate processing apparatusis programmed so that the processing liquid is supplied toward thesubstrate from the processing liquid supplying unit, the processingliquid supplied to the surface of the substrate is solidified or curedby the processing film forming unit to form, on the surface of thesubstrate, a processing film which has a high solubility solid formed bythe high solubility component and a low solubility solid formed by thelow solubility component and holds a removal object present on thesurface of the substrate, the dissolving liquid is supplied toward thesubstrate from the dissolving liquid supplying unit, the high solubilitysolid of the processing film is dissolved by the dissolving liquid, thepeeling liquid is supplied toward the substrate from the peeling liquidsupplying unit, and the processing film in a state of holding theremoval object is peeled from the surface of the substrate.

According to the present apparatus, the same effects as those of theabove-described substrate processing method are obtained.

The aforementioned and other objects, features, and effects of thepresent invention will be clarified by the following description ofpreferred embodiments, with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic plan view which shows a layout of a substrateprocessing apparatus according to a first preferred embodiment of thepresent invention.

FIG. 2 is a schematic partial sectional view which shows a generalconfiguration of a processing unit included in the substrate processingapparatus.

FIG. 3 is a schematic view which shows a droplet of pure water on asubstrate and a periphery thereof.

FIG. 4A is a schematic view for describing conditions of a surface of asubstrate which is hydrophilized by an organic solvent.

FIG. 4B is a schematic view for describing conditions of the surface ofthe substrate which is hydrophilized by an oxidizing liquid.

FIG. 5 is a block diagram which shows an electrical configuration of amain portion of the substrate processing apparatus.

FIG. 6 is an configuration example of a surface layer of a substrate tobe processed.

FIG. 7 is another configuration example of the surface layer of thesubstrate to be processed.

FIG. 8 is a flowchart for describing an example of substrate processingby the substrate processing apparatus.

FIG. 9A is a schematic view for describing conditions of ahydrophilization step (Step S2) in the substrate processing.

FIG. 9B is a schematic view for describing conditions of a first rinsingstep (Step S3) in the substrate processing.

FIG. 9C is a schematic view for describing conditions of a replacingstep (Step S4) in the substrate processing.

FIG. 9D is a schematic view for describing conditions of a processingliquid supplying step (Step S5) in the substrate processing.

FIG. 9E is a schematic view for describing conditions of a processingfilm forming step (Step S6) in the substrate processing.

FIG. 9F is a schematic view for describing conditions of the processingfilm forming step (Step S6) in the substrate processing.

FIG. 9G is a schematic view for describing conditions of a peeling step(Step S7) in the substrate processing.

FIG. 9H is a schematic view for describing conditions of a secondrinsing step (Step S8) in the substrate processing.

FIG. 9I is a schematic view for describing conditions of a residueremoving step (Step S9) in the substrate processing.

FIG. 10A is a schematic view for describing conditions in which aprocessing film is peeled from a surface of a substrate.

FIG. 10B is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate.

FIG. 10C is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate.

FIG. 11 is a flowchart for describing another example of the substrateprocessing by the substrate processing apparatus.

FIG. 12A is a schematic view for describing procedures for measuring acontact angle of pure water for a surface of an experimental substrate.

FIG. 12B is a schematic view for describing procedures for peeling aprocessing film from the experimental substrate.

FIG. 13 is a table which shows a contact angle of pure water for thesurface of the experimental substrate and whether the processing film ispeeled off by a peeling liquid.

FIG. 14 is a schematic view for describing procedures for measuring acontact angle of pure water for the surface of the processing film.

FIG. 15 is a table which shows the contact angle of pure water for thesurface of the processing film.

FIG. 16 is a schematic partial sectional view which shows a generalconfiguration of a processing unit included in a substrate processingapparatus according to a second preferred embodiment of the presentinvention.

FIG. 17 is a schematic view for describing conditions in which a surfaceof a substrate is hydrophilized by a peeling liquid.

FIG. 18 is a flowchart for describing an example of substrate processingby the substrate processing apparatus according to the second preferredembodiment.

FIG. 19A is a schematic view for describing conditions of a processingliquid supplying step (Step S22) in the substrate processing accordingto the second preferred embodiment.

FIG. 19B is a schematic view for describing conditions of a processingfilm forming step (Step S23) in the substrate processing according tothe second preferred embodiment.

FIG. 19C is a schematic view for describing conditions of a processingfilm forming step (Step S23) in the substrate processing according tothe second preferred embodiment.

FIG. 19D is a schematic view for describing conditions of a peelingliquid supplying step (Step S24) in the substrate processing accordingto the second preferred embodiment.

FIG. 19E is a schematic view for describing conditions of a rinsing step(Step S25) in the substrate processing according to the second preferredembodiment.

FIG. 19F is a schematic view for describing conditions of a residueremoving liquid supplying step (Step S26) in the substrate processingaccording to the second preferred embodiment.

FIG. 20A is a schematic view for describing conditions in which aprocessing film is peeled from a surface of a substrate.

FIG. 20B is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate.

FIG. 20C is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate.

FIG. 21 is a schematic view for describing conditions of a peelingliquid supplying step (Step S24) in the substrate processing accordingto a modified example of the substrate processing apparatus of thesecond preferred embodiment.

FIG. 22 is a schematic partial sectional view which shows a generalconfiguration of a processing unit included in a substrate processingapparatus according to a third preferred embodiment of the presentinvention.

FIG. 23 is a flowchart for describing an example of substrate processingaccording to the third preferred embodiment.

FIG. 24A is a schematic view for describing conditions of a dissolvingliquid supplying step (Step S30) in the substrate processing accordingto the third preferred embodiment.

FIG. 24B is a schematic view for describing conditions of a rinsing step(Step S31) in the substrate processing according to the third preferredembodiment.

FIG. 25A is a schematic view for describing conditions in which aprocessing film is peeled from a surface of a substrate in the substrateprocessing according to the third preferred embodiment.

FIG. 25B is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate in thesubstrate processing according to the third preferred embodiment.

FIG. 25C is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate in thesubstrate processing according to the third preferred embodiment.

FIG. 25D is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate in thesubstrate processing according to the third preferred embodiment.

FIG. 26 is a schematic partial sectional view which shows a generalconfiguration of a processing unit included in the substrate processingapparatus according to the fourth preferred embodiment of the presentinvention.

FIG. 27 is a schematic view for describing conditions in which thesurface of the substrate is hydrophilized by a hydrophilizing liquid.

FIG. 28 is a flowchart for describing an example of substrate processingaccording to a fourth preferred embodiment.

FIG. 29A is a schematic view for describing conditions of ahydrophilizing liquid supplying step (Step S40) in the substrateprocessing according to the fourth preferred embodiment.

FIG. 29B is a schematic view for describing conditions of a rinsing step(Step S41) in the substrate processing according to the fourth preferredembodiment.

FIG. 30A is a schematic view for describing conditions in which aprocessing film is peeled from a surface of a substrate in the substrateprocessing according to the fourth preferred embodiment.

FIG. 30B is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate in thesubstrate processing according to the fourth preferred embodiment.

FIG. 30C is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate in thesubstrate processing according to the fourth preferred embodiment.

FIG. 30D is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate in thesubstrate processing according to the fourth preferred embodiment.

FIG. 30E is a schematic view for describing conditions in which theprocessing film is peeled from the surface of the substrate in thesubstrate processing according to the fourth preferred embodiment.

FIG. 31 is a flowchart for describing another example of the substrateprocessing according to the fourth preferred embodiment.

FIG. 32A is a schematic view for describing conditions of a priorhydrophilization step (Step S50) executed by another example of thesubstrate processing according to the fourth preferred embodiment.

FIG. 32B is a schematic view for describing conditions of a rinsing step(Step S51) executed by another example of the substrate processingaccording to the fourth preferred embodiment.

FIG. 32C is a schematic view for describing conditions of a replacingstep (Step S52) executed by another example of the substrate processingaccording to the fourth preferred embodiment.

FIG. 33 is a graph which shows a relationship between a concentration ofIPA in diluted IPA and a contact angle of the diluted IPA for a surfacean experimental substrate.

FIG. 34 are microscopic images for describing conditions of a surface ofan experimental substrate when diluted IPA is dropped on theexperimental substrate where a processing film is formed on the surfacethereof.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Configuration ofSubstrate Processing Apparatus According to First Preferred Embodiment

FIG. 1 is a schematic plan view which shows a layout of a substrateprocessing apparatus 1 according to a preferred embodiment of thepresent invention.

The substrate processing apparatus 1 is a single substrate processingtype apparatus that processes a substrate W such as a silicon wafer,etc., one at a time. In the present preferred embodiment, the substrateW is a disc-shaped substrate.

As the substrate W, there may be used a substrate in which, at least anyone of Si (silicon), SiN (silicon nitride), SiO₂ (silicon oxide), SiGe(silicon germanium), Ge (germanium), SiCN (silicon carbonitride), W(tungsten), TiN (titanium nitride), Co (cobalt), Cu (copper), Ru(ruthenium) and a-C (amorphous carbon), is exposed on the surfacethereof. That is, only one type of the above substances may be exposedon the surface of the substrate W or, of the above-described substances,plural types of them may be exposed.

The substrate processing apparatus 1 includes a plurality of processingunits 2 for processing substrates W with fluids, load ports LP on whichare placed carriers C that house a plurality of the substrates W to beprocessed by the processing units 2, transfer robots IR and CR thattransfer the substrates W between the load ports LP and the processingunits 2, and a controller 3 which controls the substrate processingapparatus 1.

The transfer robot IR transfers the substrates W between the carriers Cand the transfer robot CR. The transfer robot CR transfers thesubstrates W between the transfer robot IR and the processing units 2.The plurality of processing units 2 have, for example, the sameconfiguration. Although the details will be described later, processingfluids supplied to the substrate W inside the processing unit 2 includea hydrophilizing liquid, a rinse liquid, a replacing liquid, aprocessing liquid, a peeling liquid, a residue removing liquid, adissolving liquid, a heating medium, an inert gas (a gas), etc.

Each processing unit 2 includes a chamber 4 and a processing cup 7disposed inside the chamber 4 and executes processing of the substrate Winside the processing cup 7. An inlet/outlet (not shown) for carrying-inthe substrate W and carrying-out the substrate W by the transfer robotCR is formed at the chamber 4. The chamber 4 is provided with a shutterunit (not shown) for opening and closing the inlet/outlet.

FIG. 2 is a schematic view for describing an configuration example ofthe processing unit 2. The processing unit 2 includes a spin chuck 5, afacing member 6, a processing cup 7, a first moving nozzle 9, a secondmoving nozzle 10, a third moving nozzle 11, a central nozzle 12 and alower surface nozzle 13.

The spin chuck 5 is an example of a substrate holding/rotating unitwhich rotates the substrate W around a rotation axis A1 (a verticalaxis) while holding the substrate W horizontally. The rotation axis A1is a vertical straight line passing through a central portion of thesubstrate W. The spin chuck 5 includes a plurality of chuck pins 20, aspin base 21, a rotating shaft 22 and a spin motor 23.

The spin base 21 has a disc shape oriented along a horizontal direction.On an upper surface of the spin base 21, a plurality of chuck pins 20which grip a peripheral edge of the substrate W are disposed atintervals in a circumferential direction of the spin base 21. The spinbase 21 and the plurality of chuck pins 20 form a substrate holding unitwhich holds the substrate W horizontally. The substrate holding unit isalso referred to as a substrate holder.

The rotating shaft 22 extends in a vertical direction along the rotationaxis A1. An upper end portion of the rotating shaft 22 is coupled to alower surface center of the spin base 21. The spin motor 23 applies arotating force to the rotating shaft 22. The spin base 21 is rotated bythe rotating shaft 22 being rotated by the spin motor 23. The substrateW is thereby rotated around the rotation axis A1. The spin motor 23 isan example of a substrate rotating unit which rotates the substrate Waround the rotation axis A1.

The spin chuck 5 is not limited to a sandwiching type chuck which allowsthe plurality of chuck pins 20 to be in contact with a circumferentialedge surface of the substrate W but may also include a vacuum type chuckby which a lower surface of the substrate W is adsorbed on an uppersurface of the spin base 21 to hold the substrate W horizontally.

The facing member 6 faces the substrate W held by the spin chuck 5 fromabove. The facing member 6 is formed in a disc shape having the diametersubstantially equal to, or larger than the substrate W. The facingmember 6 has a facing surface 6 a which faces an upper surface (surfaceon the upper side) of the substrate W. The facing surface 6 a isdisposed substantially along a horizontal surface higher than the spinchuck 5.

A hollow shaft 60 is fixed to the facing member 6 at an opposite side tothe facing surface 6 a. A communicating hole 6 b which penetrates up anddown through the facing member 6 is formed at a portion of the facingmember 6 which overlaps with the rotation axis A1 in plan view. Thecommunicating hole 6 b communicates with an internal space 60 a of thehollow shaft 60.

The facing member 6 blocks an atmosphere inside a space between thefacing surface 6 a and the upper surface of the substrate W from anatmosphere outside the space. Therefore, the facing member 6 is alsoreferred to as a blocking plate.

The processing unit 2 further includes a facing member raising/loweringunit 61 which drives raising and lowering of the facing member 6 and afacing member rotating unit 62 which rotates the facing member 6 aroundthe rotation axis A1.

The facing member raising/lowering unit 61 is capable of moving thefacing member 6 at any position (height) from a lower position to anupper position in a vertical direction. The lower position is a positionwithin a movable range of the facing member 6 at which the facingsurface 6 a is positioned closest to the substrate W. The upper positionis a position within the movable range of the facing member 6 at whichthe facing surface 6 a is separated farthest from the substrate W. Whenthe facing member 6 is positioned at the upper position, the transferrobot CR accesses the spin chuck 5 for carrying-in and carrying-out thesubstrate W.

The facing member raising/lowering unit 61 includes, for example, aball-screw mechanism (not shown) coupled to a supporting member (notshown) which supports the hollow shaft 60 and an electric motor (notshown) which applies a driving force to the ball-screw mechanism. Thefacing member raising/lowering unit 61 is also referred to as a facingmember lifter (blocking plate lifter). The facing member rotating unit62 includes a motor (not shown) which rotates, for example, the hollowshaft 60.

The processing cup 7 includes a plurality of guards 71 which receive aliquid splashed outside from the substrate W held by the spin chuck 5, aplurality of cups 72 which receive a liquid guided downward by theplurality of guards 71 and a circular-cylindrical outer wall memberwhich surrounds the plurality of guards 71 and the plurality of cups 72.

In the present preferred embodiment, an example where two guards 71 (afirst guard 71A and a second guard 71B) and two cups 72 (a first cup 72Aand a second cup 72B) are provided is shown.

Each of the first cup 72A and the second cup 72B has an annular grooveshape which is opened upward.

The first guard 71A is disposed so as to surround the spin base 21. Thesecond guard 71B is disposed so as to surround the spin base 21 atfurther outside than the first guard 71A.

Each of the first guard 71A and the second guard 71B has a substantiallycircular-cylindrical shape. An upper end portion of each of the guards71 is inclined inward so as to be directed toward the spin base 21.

The first cup 72A receives a liquid guided downward by the first guard71A. The second cup 72B is formed integral to the first guard 71A toreceive a liquid guided downward by the second guard 71B.

The processing unit 2 includes a guard raising/lowering unit 74 whichraises and lowers each of the first guard 71A and the second guard 71Bseparately in a vertical direction. The guard raising/lowering unit 74raises and lowers the first guard 71A between the lower position and theupper position. The guard raising/lowering unit 74 raises and lowers thesecond guard 71B between the lower position and the upper position.

When the first guard 71A and the second guard 71B are both positioned atthe upper position, a liquid splashed from the substrate W is receivedby the first guard 71A. When the first guard 71A is positioned at thelower position and the second guard 71B is positioned at the upperposition, a liquid splashed from the substrate W is received by thesecond guard 71B. When the first guard 71A and the second guard 71B areboth positioned at the lower position, the transfer robot CR accessesthe spin chuck 5 for carrying-in and carrying-out the substrate W.

The guard raising/lowering unit 74 includes, for example, a firstball-screw mechanism (not shown) coupled to the first guard 71A, a firstmotor (not shown) which applies a driving force to the first ball-screwmechanism, a second ball-screw mechanism (not shown) coupled to thesecond guard 71B, and a second motor (not shown) which applies a drivingforce to the second ball-screw mechanism. The guard raising/loweringunit 74 is also referred to as a guard lifter.

The first moving nozzle 9 is an example of a hydrophilizing liquidnozzle (hydrophilizing liquid supplying unit) which supplies(discharges) a hydrophilizing liquid toward the upper surface of thesubstrate W held by the spin chuck 5.

The first moving nozzle 9 is moved in a horizontal direction and in avertical direction by a first nozzle moving unit 35. The first movingnozzle 9 is capable of moving between a center position and a homeposition (retract position) in the horizontal direction. When positionedat the center position, the first moving nozzle 9 faces a central regionof the upper surface of the substrate W. The central region of the uppersurface of the substrate W is a region that includes a rotation centerof the substrate W and a periphery thereof on the upper surface of thesubstrate W.

When positioned at the home position, the first moving nozzle 9 does notface the upper surface of the substrate W but is positioned outside theprocessing cup 7 in plan view. By moving in the vertical direction, thefirst moving nozzle 9 can move close to the upper surface of thesubstrate W and retract upward from the upper surface of the substrateW.

The first nozzle moving unit 35 includes, for example, an arm (notshown) which is coupled to the first moving nozzle 9 and extendshorizontally, a turning shaft (not shown) which is coupled to the armand extends along the vertical direction and a turning shaft drivingunit (not shown) which raises, lowers and turns the turning shaft.

The turning shaft driving unit turns the turning shaft around a verticalturning axis, thereby swinging the arm. Further, the turning shaftdriving unit raises and lowers the turning shaft along the verticaldirection, thereby raising and lowering the arm. The first moving nozzle9 moves in the horizontal direction and in the vertical direction inaccordance with the swinging and raising/lowering of the arm.

The first moving nozzle 9 is connected to a hydrophilizing liquid piping40 which guides a hydrophilizing liquid. When a hydrophilizing liquidvalve 50 interposed in the hydrophilizing liquid piping 40 is opened,the hydrophilizing liquid is discharged continuously downward from thefirst moving nozzle 9. When the first moving nozzle 9 is positioned at acentral position and the hydrophilizing liquid valve 50 is opened, thehydrophilizing liquid is supplied to the central region of the uppersurface of the substrate W.

The hydrophilizing liquid discharged from the first moving nozzle 9 is,for example, an oxidizing liquid such as hydrofluoric acid (HF, DHF), anammonia-hydrogen peroxide mixture (SC1) and a sulfuric acid/hydrogenperoxide mixture (SPM), an organic solvent such as isopropyl alcohol(IPA), and a first hydrophilizing liquid such as hydrochloric acid(HCl). The hydrophilizing liquid is a liquid for hydrophilizing(enhancing hydrophilicity of) the surface of the substrate W.

The oxidizing liquid is a liquid which contains a substance (oxidizingagent) having an oxidation power. For example, SC1 contains hydrogenperoxide as an oxidizing agent, and hydrofluoric acid contains hydrogenfluoride as an oxidizing agent. SPM contains persulfuric acid as anoxidizing agent.

Hydrophilicity means an affinity for water. Hydrophilicity is alsoreferred to as wettability. A contact angle is given for indicatinghydrophilicity. The contact angle is such that an extent of swelling ofa droplet (height of liquid) formed when a liquid is dropped on acertain solid is expressed in numerals. Specifically, the contact angleis an angle formed between a liquid surface and a solid surface, whenthe liquid adhering to the surface of the solid is viewed from the side.The larger the contact angle is, the lower the wettability of thesurface of the solid is. The smaller the contact angle is, the higherthe wettability of the surface of the solid is.

FIG. 3 is a schematic view which shows a droplet of pure water on thesubstrate W and a periphery thereof. As shown in FIG. 3 , a contactangle θ of pure water for the surface of the substrate W is preferablylarger than 0° and smaller than 41.7°. In the present preferredembodiment, DIW is used as pure water. Where the contact angle of purewater for the surface of the substrate W is larger than 0° and smallerthan 41.7°, a processing film (described later) is easily peeled fromthe surface of the substrate W by a peeling liquid (described later).The contact angle θ of pure water for the surface of the substrate W ismore preferably larger than 0° and not more than 36.0°. The contactangle θ of pure water for the surface of the substrate W is even morepreferably larger than 0° and not more than 32.7°.

Next, a description will be given of conditions in which the surface ofthe substrate W is hydrophilized. FIG. 4A and FIG. 4B are each aschematic view for describing conditions in which the surface of thesubstrate W is hydrophilized by a first hydrophilizing liquid.

Where an organic solvent such as IPA is used as the first hydrophilizingliquid, a hydrophobic organic substance 170 adhering to the surface ofthe substrate W is removed, thereby hydrophilizing the surface of thesubstrate W. Specifically, as shown in FIG. 4A, the hydrophobic organicsubstance 170 present on the surface of the substrate W is dissolved inan organic solvent to hydrophilize the surface of the substrate W.Therefore, there may be a case in which an organic substance 170A whichis less likely to be dissolved in the first hydrophilizing liquidremains on the surface of the substrate W. Accordingly, hydrophilizationby an organic solvent is influenced by the type of the organic substance170 present on the surface of the substrate W.

An organic substance is one of a removal objects present on the surfaceof the substrate W, and even removal of the organic substance by anorganic solvent will not realize a sufficient removal of the removalobject. Therefore, even where the surface of the substrate W ishydrophilized by the organic solvent, as described later, it isnecessary to remove the removal object by peeling a processing film.

On the other hand, where an oxidizing liquid such as hydrofluoric acidand SC1 is used as the first hydrophilizing liquid, as shown in FIG. 4B,the surface of the substrate W is oxidized to form an oxide film 171 onthe surface of the substrate W. Due to oxidization of the surface of thesubstrate W, oxygen atoms bond to a substance exposed from the surfaceof the substrate W. Oxygen atoms bond to the substance exposed from thesurface of the substrate W, thereby improving the hydrophilicity of thesurface of the substrate W.

Where an oxidizing liquid is used as the first hydrophilizing liquid,regardless of whether the organic substance 170 is present, it ispossible to hydrophilize the surface of the substrate W. In other words,even where the organic substance 170A which is less likely to bedissolved by an organic solvent is present on the surface of thesubstrate W, it is possible to hydrophilize the surface of the substrateW. Therefore, the use of the oxidizing liquid as the firsthydrophilizing liquid enhances more efficiently the hydrophilicity ofthe surface of the substrate W than the use of the organic solvent asthe first hydrophilizing liquid.

Where the substrate W has the surface from which at least any one of Si,SiN, SiO₂, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru and a-C is exposed, thesurface can be hydrophilized by the first hydrophilizing liquid. Wherethe substrate W has the surface from which at least any one of Si, SiN,SiO₂, W, TiN, Co, Cu, Ru and a-C in particular is exposed, the surfaceis easily hydrophilized by the first hydrophilizing liquid, and wherethe substrate W has the surface from which any one of Si, SiN, SiO₂, W,TiN, Co and Cu is exposed, the surface is more likely to behydrophilized by the first hydrophilizing liquid.

Again, with reference to FIG. 2 , the second moving nozzle 10 is anexample of a processing liquid nozzle (processing liquid supplying unit)which supplies (discharges) a processing liquid toward the upper surfaceof the substrate W held by the spin chuck 5.

The second moving nozzle 10 is moved in the horizontal direction and inthe vertical direction by the second nozzle moving unit 36. The secondmoving nozzle 10 moves in the horizontal direction between the centerposition and the home position (retract position). The second movingnozzle 10 faces the central region of the upper surface of the substrateW when positioned at the center position.

When positioned at the home position, the second moving nozzle 10 doesnot face the upper surface of the substrate W and is positioned outsidethe processing cup 7 in plan view. The second moving nozzle 10 movesclose to the upper surface of the substrate W or retracts upward fromthe upper surface of the substrate W by moving in the verticaldirection.

The second nozzle moving unit 36 has the same configuration as the firstnozzle moving unit 35. That is, the second nozzle moving unit 36 mayinclude an arm (not shown) which is coupled to the second moving nozzle10 and extends horizontally, a turning shaft (not shown) coupled to thearm and extends along the vertical direction and a turning shaft drivingunit (not shown) which raises, lowers and turns the turning shaft.

The second moving nozzle 10 is connected to a processing liquid piping44 which guides a processing liquid. When a processing liquid valve 54interposed in the processing liquid piping 44 is opened, the processingliquid is continuously discharged downward from the second moving nozzle10. When the second moving nozzle 10 is positioned at the centralposition and the processing liquid valve 54 is opened, the processingliquid is supplied to the central region of the upper surface of thesubstrate W.

The processing liquid contains a solute and a solvent. The processingliquid undergoes solidification or curing by volatilization(evaporation) of at least a portion of the solvent contained in theprocessing liquid. The processing liquid is solidified or cured on thesubstrate W to form a solid processing film which holds a removal objectsuch as particles, etc., present on the substrate W.

Here, “solidification” refers, for example, to hardening of the solutedue to forces acting between molecules or between atoms, etc., inassociation with volatilization of the solvent. “Curing” refers, forexample, to hardening of the solute due to a chemical change such aspolymerization, crosslinking, etc. Therefore, “solidification or curing”expresses “hardening” of the solute due to various causes.

The processing liquid contains, as the solute, a low solubilitycomponent and a high solubility component.

The processing liquid discharged from the second moving nozzle 10 maycontain a corrosion preventive component. Although the details will bedescribed later, the corrosion preventive component is, for example, BTA(benzotriazole).

As the low solubility component and the high solubility component, theremay be used a substance which is different from each other in solubilityin a peeling liquid which will be described later. The low solubilitycomponent is, for example, novolac. The high solubility component is,for example, 2,2-bis(4-hydroxyphenyl)propane.

The solvent contained in the processing liquid may be a liquid whichdissolves the low solubility component and the high solubilitycomponent. The solvent contained in the processing liquid is preferablya liquid having compatibility (miscible) with a peeling liquid.Compatibility is a property in which two types of liquids are mutuallydissolved and mixed.

The processing film is mainly composed of a low solubility component ina solid state and a high solubility component in a solid state. Thesolvent may remain in the processing film. Details of each of thecomponents contained in the processing liquid (solvent, low solubilitycomponent, high solubility component and corrosion preventive component)will be described later.

Where the contact angle of pure water for the processing film is largerthan 52° and smaller than 61°, the peeling liquid which will bedescribed later fully acts on an interface between the substrate W andthe processing film. The use of the processing liquid which will bedescribed later forms the processing film with the contact angle of purewater larger than 52° and smaller than 61°.

The third moving nozzle 11 is an example of a peeling liquid nozzle(peeling liquid supplying unit) which continuously supplies (discharges)a peeling liquid such as ammonia water toward the upper surface of thesubstrate W held by the spin chuck 5. The peeling liquid is a liquid forpeeling the processing film in a state of holding a removal object fromthe upper surface of the substrate W.

The third moving nozzle 11 is moved in the horizontal direction and inthe vertical direction by a third nozzle moving unit 37. The thirdmoving nozzle 11 moves between the center position and the home position(retract position) in the horizontal direction.

When positioned at the center position, the third moving nozzle 11 facesthe central region of the upper surface of the substrate W. Whenpositioned at the home position, the third moving nozzle 11 does notface the upper surface of the substrate W and is positioned outside theprocessing space 7 in plan view. The third moving nozzle 11 moves closeto the upper surface of the substrate W and retracts upward from theupper surface of the substrate W by moving in the vertical direction.

The third nozzle moving unit 37 has the same configuration as the firstnozzle moving unit 35. That is, the third nozzle moving unit 37 mayinclude an arm (not shown) which is coupled to the third moving nozzle11 and extends horizontally, a turning shaft (not shown) which iscoupled to the arm and extends along the vertical direction and aturning shaft driving unit (not shown) which raises, lowers and turnsthe turning shaft.

The third moving nozzle 11 is connected to an upper peeling liquidpiping 45 which guides a peeling liquid to the third moving nozzle 11.When an upper peeling liquid valve 55 interposed in the upper peelingliquid piping 45 is opened, the peeling liquid is continuouslydischarged downward from a discharge port of the third moving nozzle 11.When the third moving nozzle 11 is positioned at the central positionand the upper peeling liquid valve 55 is opened, the peeling liquid issupplied to the central region of the upper surface of the substrate W.

In the present preferred embodiment, as the peeling liquid, a firstpeeling liquid is used. As the first peeling liquid, a liquid which ismore likely to dissolve a high solubility component contained in theprocessing liquid than a low solubility component contained in theprocessing liquid is used. The first peeling liquid is, for example,ammonia water and a mass percent concentration of ammonia in the peelingliquid is 0.4%.

The first peeling liquid may be, for example, an alkaline aqueoussolution (alkaline liquid) other than ammonia water. Specific examplesof the alkaline aqueous solution other than ammonia water include TMAH(tetramethylammonium hydroxide) aqueous solution, a choline aqueoussolution and a combination of any of them. The first peeling liquid maybe pure water (preferably DIW) or may be a neutral or an acidic aqueoussolution (non-alkaline aqueous solution).

The first peeling liquid is preferably alkaline. The first peelingliquid is preferably 7˜13 in pH. In detail, the first peeling liquid ispreferably 8˜13 in pH, more preferably 10˜13 and even more preferably11˜12.5. The pH is preferably measured after degassing for avoidinginfluence due to dissolution of carbon dioxide in air.

A large portion of the solvent of the first peeling liquid is purewater. A percentage of pure water contained in the solvent of the firstpeeling liquid is 50˜100 mass % (preferably 70 mass %˜100 mass %, morepreferably 90 mass %˜100 mass %, even more preferably 95 mass %˜100 mass% and yet even more preferably 99˜100 mass %). “Mass %” is a percentageof a mass of a certain component with respect to a total mass of aliquid. A mass percent concentration of the solute of the first peelingliquid is 0.1%˜10% (preferably 0.2%˜8% and more preferably 0.3%˜6%).

The central nozzle 12 is housed in the internal space 60 a of the hollowshaft 60 of the facing member 6. A discharge port 12 a provided at a tipof the central nozzle 12 is exposed from a communicating hole 6 b andfaces the central region of the upper surface of the substrate W fromabove.

The central nozzle 12 includes a plurality of tubes (a first tube 31, asecond tube 32 and a third tube 33) which discharge a fluid downward anda cylindrical casing 30 which surrounds the plurality of tubes. Theplurality of tubes and the casing 30 extend in an up/down directionalong the rotation axis A1. The discharge port 12 a of the centralnozzle 12 also serves as a discharge port of the first tube 31, adischarge port of the second tube 32 and a discharge port of the thirdtube 33.

The first tube 31 (central nozzle 12) is an example of a rinse liquidsupplying unit which supplies a rinse liquid such as DIW to the uppersurface of the substrate W. The second tube 32 (central nozzle 12) is anexample of an organic solvent supplying unit which supplies an organicsolvent such as IPA to the upper surface of the substrate W. The thirdtube 33 (central nozzle 12) is an example of a gas supplying unit whichsupplies a gas such as nitrogen gas (N₂) between the upper surface ofthe substrate W and a facing surface 6 a of the facing member 6. Thecentral nozzle 12 serves also as a rinse liquid nozzle, an organicsolvent nozzle and a gas nozzle.

The first tube 31 is connected to an upper rinse liquid piping 41 whichguides a rinse liquid to the first tube 31. When an upper rinse liquidvalve 51 which is interposed in the upper rinse liquid piping 41 isopened, the rinse liquid is continuously discharged toward the centralregion of the upper surface of the substrate W from the first tube 31(central nozzle 12).

The rinse liquid is a liquid for washing away a liquid adhering to thesurface of the substrate W. As the rinse liquid, included are DIW,carbonated water, electrolyzed ion water, hydrochloric acid water with adilution concentration (for example, approximately 1 ppm 100 ppm),ammonia water with a dilution concentration (for example, approximately1 ppm˜100 ppm) and reduced water (hydrogen water).

The second tube 32 is connected to an organic solvent piping 42 whichguides an organic solvent such as IPA to the second tube 32. When anorganic solvent valve 52 interposed in the organic solvent piping 42 isopened, the organic solvent is continuously discharged toward thecentral region of the upper surface of the substrate W from the secondtube 32 (central nozzle 12).

The organic solvent discharged from the second tube 32 preferably hascompatibility with the rinse liquid and the processing liquid. Theorganic solvent discharged from the second tube 32 functions as aresidue removing liquid which dissolves and removes a residue of theprocessing film remaining on the upper surface of the substrate W, afterthe processing film is peeled and removed from the upper surface of thesubstrate W by a peeling liquid. Thus, the residue removing liquid isalso referred to as a residue dissolving liquid.

In the substrate processing which will be described later, an organicsolvent discharged from the second tube 32 is supplied to the uppersurface of the substrate W covered with a liquid film of the rinseliquid, and a processing liquid is supplied to the upper surface of thesubstrate W covered with a liquid film of the organic solvent. When theorganic solvent is supplied to the upper surface of the substrate Wcovered with the liquid film of the rinse liquid, a large portion of therinse liquid on the substrate W is rinsed by the organic solvent andexpelled from the substrate W. A trace amount of the remaining rinseliquid dissolves in the organic solvent and diffuses into the organicsolvent. The diffused rinse liquid is expelled from the substrate Wtogether with the organic solvent. Therefore, it is possible toefficiently replace the rinse liquid on the substrate W with the organicsolvent. Due to the same reason, it is possible to efficiently replacethe organic solvent on the substrate W with the processing liquid.Thereby, it is possible to reduce an amount of the rinse liquidcontained in the processing liquid on the substrate W. The organicsolvent which is discharged from the second tube 32 functions as areplacing liquid for replacing the rinse liquid.

Further, the organic solvent discharged from the second tube 32 ispreferably a low surface tension liquid which is lower in surfacetension than the rinse liquid. In the substrate processing which will bedescribed later, the upper surface of the substrate W is not dried byspinning off the rinse liquid on the substrate W, but the rinse liquidon the substrate W is replaced with an organic solvent and, thereafter,the organic solvent on the substrate W is spun off to dry the uppersurface of the substrate W. Therefore, if the organic solvent is a lowsurface tension liquid, it is possible to lower a surface tension whichacts on the upper surface of the substrate W upon drying of the uppersurface of the substrate W.

As the organic solvent which functions as a residue removing liquid, alow surface tension liquid and a replacing liquid, a liquid, etc., thatcontains at least one of IPA, HFE (hydrofluoroether), methanol, ethanol,acetone, PGEE (propylene glycol monoethyl ether) andtrans-1,2-dichloroethylene can be cited.

The organic solvent which functions as a residue removing liquid, a lowsurface tension liquid and a replacing liquid is not necessarilycomposed of a single component alone but may be a liquid which is mixedwith other components. It may be, for example, a liquid mixture of IPAand DIW or a liquid mixture of IPA and HFE.

The third tube 33 is connected to a gas piping 43 which guides a gas tothe third tube 33. When a gas valve 53 which is interposed in the gaspiping 43 is opened, the gas is continuously discharged downward fromthe third tube 33 (central nozzle 12).

The gas discharged from the third tube 33 is, for example, an inert gassuch as nitrogen gas. The gas discharged from the third tube 33 may beair. The inert gas is not limited to nitrogen gas but is a gas inert tothe upper surface of the substrate W. As examples of the inert gas, raregases such as argon are cited, in addition to nitrogen gas.

The lower surface nozzle 13 is inserted into a penetrating hole 21 awhich is opened at the central portion of the upper surface of the spinbase 21. A discharge port 13 a of the lower surface nozzle 13 is exposedfrom an upper surface of the spin base 21. The discharge port 13 a ofthe lower surface nozzle 13 opposes a central region of a lower surface(a surface on the lower side) of the substrate W from below. The centralregion of the lower surface of the substrate W is a region of the lowersurface of the substrate W which includes a rotation center of thesubstrate W.

One end of a common piping 80 which commonly guides a rinse liquid, apeeling liquid and a heating medium to the lower surface nozzle 13 isconnected to the lower surface nozzle 13. The other end of the commonpiping 80 is connected to a lower rinse liquid piping 81 which guidesthe rinse liquid to the common piping 80, a lower peeling liquid piping82 which guides the peeling liquid to the common piping 80 and a heatingmedium piping 83 which guides the heating medium to the common piping80.

When a lower rinse liquid valve 86 which is interposed in the lowerrinse liquid piping 81 is opened, the rinse liquid is continuouslydischarged toward the central region of the lower surface of thesubstrate W from the lower surface nozzle 13. When a lower peelingliquid valve 87 which is interposed in the lower peeling liquid piping82 is opened, the peeling liquid is continuously discharged toward thecentral region of the lower surface of the substrate W from the lowersurface nozzle 13. When a heating medium valve 88 which is interposed inthe heating medium piping 83 is opened, the heating medium iscontinuously discharged toward the central region of the lower surfaceof the substrate W from the lower surface nozzle 13.

The lower surface nozzle 13 is an example of a lower rinse liquidsupplying unit which supplies the rinse liquid to the lower surface ofthe substrate W. Further, the lower surface nozzle 13 is an example of alower peeling liquid supplying unit which supplies the peeling liquid tothe lower surface of the substrate W. Still further, the lower surfacenozzle 13 is an example of a heating medium supplying unit whichsupplies the heating medium to the substrate W for heating the substrateW. The lower surface nozzle 13 is also a substrate heating unit whichheats the substrate W.

The rinse liquid discharged from the lower surface nozzle 13 is the sameas the rinse liquid discharged from the central nozzle 12 and,therefore, a description thereof is omitted. The peeling liquiddischarged from the lower surface nozzle 13 is the same as the firstpeeling liquid discharged from the third moving nozzle 11 and,therefore, a description thereof is omitted.

The heating medium discharged from the lower surface nozzle 13 is, forexample, high temperature DIW, the temperature of which is higher thanroom temperature and lower than a boiling point of the solvent containedin the processing liquid. Where the solvent contained in the processingliquid is IPA, for example, DIW with a temperature of 60° C.˜80° C. isused as the heating medium. The heating medium discharged from the lowersurface nozzle 13 is not limited to high temperature DIW and may be ahigh temperature inert gas and a high temperature gas such as hightemperature air, the temperature of which is higher than roomtemperature and lower than a boiling point of the solvent contained inthe processing liquid.

FIG. 5 is a block diagram which shows an electrical configuration of amain portion of the substrate processing apparatus 1. The controller 3is provided with a microcomputer and controls a control target installedin the substrate processing apparatus 1 according to predeterminedcontrol programs.

Specifically, the controller 3 includes a processor (SPACE) 3A and amemory 3B in which the control programs are housed. The controller 3 isconfigured so as to provide various types of control for substrateprocessing according to the control programs executed by the processor3A.

The controller 3 is programmed, in particular, so as to control thetransfer robots IR, CR, the spin motor 23, the first nozzle moving unit35, the second nozzle moving unit 36, the third nozzle moving unit 37,the facing member raising/lowering unit 61, the facing member rotatingunit 62, the guard raising/lowering unit 74, the hydrophilizing liquidvalve 50, the upper rinse liquid valve 51, the organic solvent valve 52,the gas valve 53, the processing liquid valve 54, the upper peelingliquid valve 55, the lower rinse liquid valve 86, the lower peelingliquid valve 87 and the heating medium valve 88. The controller 3controls valves, thereby controlling the presence/non-presence of aprocessing fluid discharged from a corresponding nozzle and a flow rateof the processing fluid discharged from the corresponding nozzle.

<Configuration of Substrate to be Processed>

FIG. 6 shows an example of details of a surface layer of the substrate Wwhich is to be processed by the substrate processing apparatus 1. Asemiconductor layer 151, an insulation layer 152 and a barrier layer 153are provided on a surface layer 150 of the substrate W. Thesemiconductor layer 151 is formed, for example, with Si (silicon). Animpurity region 154 is formed in a surface layer portion of thesemiconductor layer 151.

The insulation layer 152 is formed, for example, with SiO₂ (siliconoxide). A contact hole 155 which penetrates through the insulation layer152 is provided above the impurity region 154.

The barrier layer 153 is formed on an upper surface of the insulationlayer 152 and an inner surface of the contact hole 155. The barrierlayer 153 is a TiN layer formed with TiN (titanium nitride) and formedby an ALD (atomic layer deposition) method, etc. Therefore, TiN isexposed on the surface of the substrate W.

The contact holes 155 may be provided at equal intervals on theinsulation layer 152, and a fine pattern, having protrusions andrecesses, may be formed by the insulation layer 152 and the contact hole155. In this case, the barrier layer 153 has a shape which follows thepattern.

FIG. 7 shows another example of details of the surface layer of thesubstrate W which is to be processed by the substrate processingapparatus 1. On the surface layer 150 of the substrate W which is to beprocessed by the substrate processing apparatus 1, as shown in FIG. 7 ,in addition to the semiconductor layer 151, the insulation layer 152 andthe barrier layer 153, a metal layer 156 may be provided. The metallayer 156 is, for example, a tungsten layer formed with W (tungsten) andformed by a CVD (chemical vapor deposition) method, etc. The metal layer156 fills the contact hole 155 and covers the barrier layer 153.Therefore, the surface of the metal layer 156 is a flat surface. A metalwhich forms the metal layer 156 is exposed on the surface of thesubstrate W shown in FIG. 7 . Where the metal layer 156 is formed withtungsten, tungsten is exposed on the surface of the substrate W.

Substrate Processing According to First Preferred Embodiment

FIG. 8 is a flowchart for describing an example of substrate processingby the substrate processing apparatus 1. FIG. 8 mainly shows processingwhich is realized by execution of programs by the controller 3. FIG.9A˜FIG. 9I are each a schematic view for describing conditions inindividual steps of the substrate processing.

In the substrate processing by the substrate processing apparatus 1, forexample, as shown in FIG. 8 , a substrate carry-in step (Step S1), ahydrophilization step (Step S2), a first rinsing step (Step S3), areplacing step (Step S4), a processing liquid supplying step (Step S5),a processing film forming step (Step S6), a peeling step (Step S7), asecond rinsing step (Step S8), a residue removing step (Step S9), a spindrying step (Step S10) and a substrate carry-out step (Step S11) areexecuted in this order.

Hereinafter, reference is made mainly to FIG. 2 and FIG. 8 . Referenceis made to FIG. 9A˜FIG. 9I, whenever necessary.

First, an unprocessed substrate W is carried from a carrier C to theprocessing unit 2 by the transfer robots IR, CR (refer to FIG. 1 ) andtransferred to the spin chuck 5 (Step S1). The substrate W is therebyheld horizontally by the spin chuck 5 (substrate holding step). When thesubstrate W is carried in, the facing member 6 is retracted at the upperposition.

The holding of the substrate W by the spin chuck 5 is continued untilthe spin drying step (Step S10) ends. During a period from the start ofthe substrate holding step to the end of the spin drying step (StepS10), the guard raising/lowering unit 74 adjusts a height position ofthe first guard 71A and that of the second guard 71B so that at leastone of the guards 71 is positioned at the upper position.

In a state that the substrate W is held by the spin chuck 5, the spinmotor 23 rotates the spin base 21. Thereby, the rotation of thesubstrate W which is held horizontally is started (substrate rotatingstep). The facing member rotating unit 62 may rotate the facing member 6synchronously with the spin base 21. Synchronous rotation is to rotatethe facing member 6 in the same rotating direction and at the samerotational speed as the spin base 21.

Next, after the transfer robot CR has been retracted outside theprocessing unit 2, the hydrophilization step (Step S2) is started. Inthe hydrophilization step, first, in a state that the facing member 6 ispositioned at the retract position, the first nozzle moving unit 35moves the first moving nozzle 9 to a processing position. The processingposition of the first moving nozzle 9 is, for example, a centralposition. When the facing member 6 is positioned at the retractposition, each moving nozzle moves horizontally between the facingmember 6 and the substrate W. The retract position may be an upperposition.

Then, the hydrophilizing liquid valve 50 is opened. Thereby, as shown inFIG. 9A, the first hydrophilizing liquid such as hydrofluoric acid issupplied (discharged) from the first moving nozzle 9 toward the centralregion of the upper surface of the substrate W in the rotating state(hydrophilizing liquid supplying step, hydrophilizing liquid dischargingstep). The first hydrophilizing liquid supplied to the upper surface ofthe substrate W spreads radially by receiving a centrifugal force andspreads over the entire upper surface of the substrate W. The uppersurface of the substrate W is thereby hydrophilized, and the contactangle of pure water for the upper surface of the substrate W becomessmaller than 41.7° (contact angle reducing step).

The supply of the first hydrophilizing liquid from the first movingnozzle 9 is continued for a predetermined time of, for example, 30seconds. In the hydrophilization step, the substrate W is rotated at apredetermined hydrophilization rotational speed of, for example, 800rpm.

Next, the first rinsing step (Step S3) which washes away the firsthydrophilizing liquid on the substrate W is executed.

Specifically, the hydrophilizing liquid valve 50 is closed. Thereby, thesupply of the first hydrophilizing liquid to the substrate W is stopped.Then, the first nozzle moving unit 35 moves the first moving nozzle 9 tothe home position. The facing member raising/lowering unit 61 then movesthe facing member 6 to the processing position between the upperposition and the lower position. When the facing member 6 is positionedat the processing position, a distance between the upper surface of thesubstrate W and the facing surface 6 a is, for example, 30 mm.

In a state that the facing member 6 is positioned at the processingposition, the upper rinse liquid valve 51 is opened. As shown in FIG.9B, the rinse liquid is thereby supplied (discharged) from the centralnozzle 12 toward the central region of the upper surface of thesubstrate W in the rotating state. The rinse liquid which is suppliedfrom the central nozzle 12 to the upper surface of the substrate Wspreads radially by receiving a centrifugal force and spreads over theentire upper surface of the substrate W. Thereby, the firsthydrophilizing liquid on the upper surface of the substrate W is washedaway outside the substrate W.

Almost at the same time with opening of the upper rinse liquid valve 51,the lower rinse liquid valve 86 is opened. As shown in FIG. 9B, therinse liquid is supplied (discharged) from the lower surface nozzle 13toward the central region of the lower surface of the substrate W in therotating state. The rinse liquid supplied from the lower surface nozzle13 to the lower surface of the substrate W spreads radially by receivinga centrifugal force and spreads over the entire lower surface of thesubstrate W. In the hydrophilization step which has been describedpreviously, even where the first hydrophilizing liquid adhering to theupper surface of the substrate W is splashed from the substrate W andadheres to the lower surface of the substrate W, the firsthydrophilizing liquid adhering to the lower surface is washed away bythe rinse liquid supplied from the lower surface nozzle 13.

The discharge of the rinse liquid from the central nozzle 12 and thelower surface nozzle 13 is continued for a predetermined time of, forexample, 30 seconds. In the first rinsing step, the substrate W isrotated at a predetermined first rinsing rotational speed of, forexample, 800 rpm.

Next, the replacing step (Step S4) is started. In the replacing step,the rinse liquid on the substrate W is replaced with the organic solvent(for example, IPA) as a replacing liquid.

Specifically, the upper rinse liquid valve 51 and the lower rinse liquidvalve 86 are closed. Thereby, the supply of the rinse liquid to theupper surface and the lower surface of the substrate W is stopped. Thefacing member 6 is kept at the processing position.

In a state that the facing member 6 is kept at the processing position,the organic solvent valve 52 is opened. Thereby, as shown in FIG. 9C,the organic solvent as the replacing liquid is supplied (discharged)from the central nozzle 12 toward the central region of the uppersurface of the substrate W in the rotating state (replacing liquidsupplying step, replacing liquid discharging step). The central nozzle12 is an example of a replacing liquid nozzle.

The organic solvent supplied from the central nozzle 12 to the uppersurface of the substrate W spreads radially by receiving a centrifugalforce and spreads over the entire upper surface of the substrate W. Therinse liquid on the substrate W is thereby replaced with the organicsolvent.

In the replacing step, the discharge of the organic solvent from thecentral nozzle 12 is continued for a predetermined time of, for example,10 seconds. In the replacing step, the substrate W is rotated at apredetermined replacing rotational speed of, for example, 300 rpm˜1500rpm. In the replacing step, it is not necessary to rotate the substrateW at a fixed rotational speed. For example, the spin motor 23 may rotatethe substrate W at 300 rpm at the start of supplying the organic solventand may accelerate the rotation of the substrate W until the rotationalspeed of the substrate W reaches 1500 rpm while the organic solvent isbeing supplied to the substrate W.

Next, the processing liquid supplying step (Step S5) which supplies theprocessing liquid to the upper surface of the substrate W is executed.Specifically, the organic solvent valve 52 is closed, and the facingmember raising/lowering unit 61 moves the facing member 6 to the retractposition. In a state that the facing member 6 is positioned at theretract position, the second nozzle moving unit 36 moves the secondmoving nozzle 10 to the processing position. The processing position ofthe second moving nozzle 10 is, for example, a central position. Then,the processing liquid valve 54 is opened. As shown in FIG. 9D, aprocessing liquid is thereby supplied (discharged) from the secondmoving nozzle 10 toward the central region of the upper surface of thesubstrate W in the rotating state (processing liquid supplying step,processing liquid discharging step). The processing liquid supplied tothe upper surface of the substrate W spreads over the entire substrate Wby a centrifugal force. Thereby, a liquid film 101 (processing liquidfilm) of the processing liquid is formed on the substrate W (processingliquid film forming step).

The supply of the processing liquid from the second moving nozzle 10 iscontinued for a predetermined time of, for example, 2 seconds˜4 seconds.In the processing liquid supplying step, the substrate W is rotated at apredetermined processing liquid rotational speed of, for example, 10rpm˜1500 rpm.

Next, the processing film forming step (Step S8) shown in FIG. 9E andFIG. 9F is executed. In the processing film forming step, the processingliquid on the substrate W is solidified or cured to form, on the uppersurface of the substrate W, a processing film 100 (refer to FIG. 9F)which holds a removal object present on the substrate W.

In the processing film forming step, first, a processing liquid filmthinning step (processing liquid spin off step) in which the liquid film101 of the processing liquid on the substrate W is made thin inthickness is executed. Specifically, the processing liquid valve 54 isclosed. Thereby, the supply of the processing liquid to the substrate Wis stopped. Then, the second moving nozzle 10 is moved to the homeposition by the second nozzle moving unit 36.

As shown in FIG. 9E, in the processing liquid film thinning step, thesubstrate W is rotated in a state that the supply of the processingliquid to the upper surface of the substrate W is stopped. Therefore,the processing liquid is partially removed from the upper surface of thesubstrate W. Thereby, the liquid film 101 on the substrate W is madeappropriate in thickness. After movement of the second moving nozzle 10to the home position, the facing member 6 is kept in the retractposition.

In the processing liquid film thinning step, the spin motor 23 changesthe rotational speed of the substrate W to a predetermined processingliquid film thinning speed. The processing liquid film thinning speedis, for example, 300 rpm˜1500 rpm. The rotational speed of the substrateW may be kept fixed within a range of 300 rpm˜1500 rpm or may be changedwithin a range of 300 rpm˜1500 rpm, whenever necessary, during theprocessing liquid film thinning step. The processing liquid filmthinning step is executed for a predetermined time of, for example, 30seconds.

In the processing film forming step, after the processing liquid filmthinning step, a processing liquid solvent evaporation step in which thesolvent is partially evaporated (volatilized) from the liquid film 101of the processing liquid is executed. In the processing liquid solventevaporation step, the liquid film 101 on the substrate W is heated forpartially evaporating the solvent of the processing liquid on thesubstrate W.

Specifically, as shown in FIG. 9F, the facing member raising/loweringunit 61 moves the facing member 6 to a proximity position. The proximityposition may be the lower position. The proximity position is a positionwhere a distance from the upper surface of the substrate W to the facingsurface 6 a is, for example, 1 mm.

Then, the gas valve 53 is opened. Thereby, the gas is supplied to aspace between the upper surface of the substrate W (the upper surface ofthe liquid film 101) and the facing surface 6 a of the facing member 6(gas supplying step).

Evaporation (volatilization) of the solvent in the liquid film 101 ispromoted by the gas blown onto the liquid film 101 on the substrate W(processing liquid solvent evaporation step, processing liquid solventevaporation promoting step). A time required to form the processing film100 can thus be reduced. In the processing film forming step, thecentral nozzle 12 functions as an evaporation unit (evaporationpromoting unit) for evaporating the solvent in the processing liquid.

Even after the processing liquid has been partially removed from thesubstrate W by the processing liquid film thinning step of the liquidfilm 101, the facing member 6 and the substrate W are continuouslyrotated. Therefore, a centrifugal force resulting from the rotation ofthe facing member 6 and the substrate W acts on the gas discharged fromthe central nozzle 12. A gas stream in which the gas moves from a centerside of the substrate W to a peripheral edge side is formed due toaction of the centrifugal force. Therefore, elimination of the gaseoussolvent in contact with the liquid film 101 from a space between thefacing member 6 and the substrate W is promoted. Evaporation of thesolvent in the liquid film 101 is thus promoted. As described above, thefacing member 6 and the spin motor 23 function as an evaporation unit(evaporation promoting unit) which evaporates (volatilizes) the solventin a processing liquid. Only the substrate W may be rotated, while thefacing member 6 is not rotated.

Also, the heating medium valve 88 is opened. Thereby, the heating mediumis supplied (discharged) from the lower surface nozzle 13 toward thecentral region of the lower surface of the substrate W in the rotatingstate (heating medium supplying step, heating medium discharging step).The heating medium supplied from the lower surface nozzle 13 to thelower surface of the substrate W spreads radially by receiving acentrifugal force and spreads over the entire lower surface of thesubstrate W.

The supply of the heating medium to the substrate W is continued for apredetermined time of, for example, 60 seconds. In the processing liquidsolvent evaporation step, the substrate W is rotated at a predeterminedevaporation rotational speed of, for example, 1000 rpm.

The heating medium is supplied to the lower surface of the substrate W,by which the liquid film 101 on the substrate W is heated via thesubstrate W. Evaporation (volatilization) of the solvent in the liquidfilm 101 is thereby promoted (processing liquid solvent evaporationstep, processing liquid solvent evaporation promoting step). A timerequired to form the processing film 100 can thus be reduced. In theprocessing film forming step as well, the lower surface nozzle 13functions as an evaporation unit (evaporation promoting unit) forevaporating (volatilizing) the solvent in the processing liquid.

By executing the processing liquid film thinning step and the processingliquid solvent evaporation step, the processing liquid is solidified orcured. The processing film 100 which holds a removal object is, thus,formed on the entire upper surface of the substrate W.

As described above, the substrate rotating unit (spin motor 23), thefacing member rotating unit 62, the central nozzle 12 and the lowersurface nozzle 13 form a processing film forming unit in which theprocessing liquid is solidified or cured to form the processing film 100in a solid state.

Gas blowing, rotation of the substrate W and heating of the substrate Wcan be used to quickly form the processing film 100. However, it is alsopossible to form the processing film 100 by the gas blowing and rotationof the substrate W. In other words, heating by the heating medium is notalways necessary in formation of the processing film 100. Therefore, thesupply of the heating medium to the substrate W may be omitted.

In the processing liquid solvent evaporation step, the substrate W ispreferably heated so that a temperature of the substrate W may be lessthan a boiling point of the solvent. The substrate W is heated to atemperature less than the boiling point of the solvent, by whichexcessive evaporation of the solvent can be suppressed and the solventremains appropriately in the processing film 100. Thereby, in comparisonto a case in which no solvent remains inside the processing film 100,the first peeling liquid easily acts on the processing film 100 in thesubsequent peeling step (Step S6).

Next, the peeling step (Step S6) of peeling the processing film 100 isexecuted. Specifically, the heating medium valve 88 is closed. Thereby,the supply of the heating medium to the lower surface of the substrate Wis stopped. The gas valve 53 is also closed. Thereby, the supply of thegas to a space between the facing surface 6 a of the facing member 6 andthe upper surface of the substrate W is stopped.

Then, the facing member raising/lowering unit 61 moves the facing member6 to the retract position. In a state that the facing member 6 ispositioned at the retract position, the third nozzle moving unit 37moves the third moving nozzle 11 to the processing position. Theprocessing position of the third moving nozzle 11 is, for example, acentral position.

Then, in a state that the third moving nozzle 11 is positioned at theprocessing position, the upper peeling liquid valve 55 is opened.Thereby, as shown in FIG. 9G, the first peeling liquid is supplied(discharged) from the third moving nozzle 11 toward the central regionof the upper surface of the substrate W in the rotating state (upperpeeling liquid supplying step, upper peeling liquid discharging step).The first peeling liquid supplied to the upper surface of the substrateW spreads over the entire upper surface of the substrate W by acentrifugal force. Thereby, the processing film 100 on the upper surfaceof the substrate W is peeled and expelled outside the substrate W,together with the first peeling liquid.

At the same time when the upper peeling liquid valve 55 is opened, thelower peeling liquid valve 87 is opened. Thereby, as shown in FIG. 9G,the first peeling liquid is supplied (discharged) from the lower surfacenozzle 13 toward the central region of the lower surface of thesubstrate W in the rotating state (lower peeling liquid supplying step,lower peeling liquid discharging step). The first peeling liquidsupplied to the lower surface of the substrate W spreads over the entirelower surface of the substrate W by a centrifugal force.

The supply of the first peeling liquid to the upper surface and thelower surface of the substrate W is continued for a predetermined timeof, for example, 60 seconds. In the peeling step, the substrate W isrotated at a predetermined peeling rotational speed of, for example, 800rpm.

Here, in the processing liquid supplying step (Step S5) shown in FIG.9D, there may be a case in which the processing liquid supplied to theupper surface of the substrate W adheres to the lower surface of thesubstrate W via a peripheral edge of the substrate W and the processingliquid adhering to the lower surface of the substrate W is solidified orcured to form a solid.

As shown in FIG. 9G, while the first peeling liquid is supplied to theupper surface of the substrate W in the peeling step (Step S6), thefirst peeling liquid is supplied (discharged) from the lower surfacenozzle 13 to the lower surface of the substrate W. Therefore, even in acase in which a solid of the processing liquid is formed on the lowersurface of the substrate W, the solid can be peeled and removed from thelower surface of the substrate W.

After the peeling step (Step S6), the second rinsing step (Step S7) inwhich the first peeling liquid is washed away from the substrate W bythe rinse liquid is executed. Specifically, the upper peeling liquidvalve 55 and the lower peeling liquid valve 87 are closed. Thereby, thesupply of the first peeling liquid to the upper surface and the lowersurface of the substrate W is stopped. Then, the third nozzle movingunit 37 moves the third moving nozzle 11 to the home position. Then, asshown in FIG. 9H, the facing member raising/lowering unit 61 moves thefacing member 6 to the processing position.

Then, in a state that the facing member 6 is positioned at theprocessing position, the upper rinse liquid valve 51 is opened. Thereby,as shown in FIG. 9H, the rinse liquid is supplied (discharged) from thecentral nozzle 12 toward the central region of the upper surface of thesubstrate W in the rotating state (upper rinse liquid supplying step,upper rinse liquid discharging step). The rinse liquid supplied to theupper surface of the substrate W spreads over the entire upper surfaceof the substrate W by a centrifugal force. Thereby, the first peelingliquid adhering to the upper surface of the substrate W is washed awayby the rinse liquid (rinsing step).

Further, at the same time when the upper rinse liquid valve 51 isopened, the lower rinse liquid valve 86 is opened. Thereby, as shown inFIG. 9H, the rinse liquid is supplied (discharged) from the lowersurface nozzle 13 toward the central region of the lower surface of thesubstrate W in the rotating state (lower rinse liquid supplying step,lower rinse liquid discharging step). Thereby, the first peeling liquidadhering to the lower surface of the substrate W is washed away by therinse liquid.

The supply of the rinse liquid to the upper surface and the lowersurface of the substrate W is continued for a predetermined time of, forexample, 30 seconds. In the second rinsing step, the substrate W isrotated for a predetermined second rinsing rotational speed of, forexample, 800 rpm.

Next, the residue removing step (Step S8) is executed. In the residueremoving step, after the peeling step, a residue of the processing film100 remaining on the upper surface of the substrate W is removed by theorganic solvent (for example, IPA) as a residue removing liquid.Specifically, the upper rinse liquid valve 51 and the lower rinse liquidvalve 86 are closed. Thereby, the supply of the rinse liquid to theupper surface and the lower surface of the substrate W is stopped.

Then, in a state that the facing member 6 is positioned at theprocessing position, the organic solvent valve 52 is opened. Thereby, asshown in FIG. 9I, the organic solvent as the residue removing liquid issupplied (discharged) from the central nozzle 12 toward the centralregion of the upper surface of the substrate W in the rotating state(residue removing liquid supplying step, residue removing liquiddischarging step).

The organic solvent supplied from the central nozzle 12 to the uppersurface of the substrate W spreads radially by receiving a centrifugalforce and spreads over the entire upper surface of the substrate W. Theorganic solvent dissolves a residue of the processing film remaining onthe upper surface of the substrate W and, thereafter, is expelled from aperipheral edge of the upper surface of the substrate W. The centralnozzle 12 is an example of the residue removing liquid nozzle.

In the residue removing step, the discharge of the organic solvent fromthe central nozzle 12 is continued for a predetermined time of, forexample, 30 seconds. In the residue removing step, the substrate W isrotated at a predetermined residue removing rotational speed of, forexample, 300 rpm.

Next, the spin drying step (Step S10) in which the substrate W isrotated at a high speed to dry the upper surface of the substrate W isexecuted.

Specifically, the organic solvent valve 52 is closed. Thereby, thesupply of the organic solvent to the upper surface of the substrate W isstopped. Then, the facing member raising/lowering unit 61 moves thefacing member 6 to a drying position lower than the processing position.When the facing member 6 is positioned at the drying position, adistance between the facing surface 6 a of the facing member 6 and theupper surface of the substrate W is, for example, 1.5 mm. Then, the gasvalve 53 is opened. Thereby, the gas is supplied to a space between theupper surface of the substrate W and the facing surface 6 a of thefacing member 6.

Then, the spin motor 23 accelerates the rotation of the substrate W torotate the substrate W at a high speed. The substrate W in the spindrying step is rotated at a drying speed of, for example, 1500 rpm. Thespin drying step is executed for a predetermined time of, for example,30 seconds. Thereby, a large centrifugal force is applied to the organicsolvent on the substrate W, and the organic solvent on the substrate Wis spun off around the substrate W. In the spin drying step, the gas issupplied to a space between the upper surface of the substrate W and thefacing surface 6 a of the facing member 6, thereby promoting theevaporation of the organic solvent.

Then, the spin motor 23 stops the rotation of the substrate W. The guardraising/lowering unit 74 moves the first guard 71A and the second guard71B to a lower position. The gas valve 53 is closed. Then, the facingmember raising/lowering unit 61 moves the facing member 6 to an upperposition.

The transfer robot CR enters the processing unit 2, scoops up aprocessed substrate W from the chuck pin 20 of the spin chuck 5 andcarries it outside the processing unit 2 (Step S11). The substrate W istransferred from the transfer robot CR to the transfer robot IR andhoused in a carrier C by the transfer robot IR.

Conditions of Peeling Processing Film in First Preferred Embodiment

Conditions of removing the processing film 100 will be described indetail, with reference to FIG. 10A FIG. 10C. FIG. 10A˜FIG. 10C are eacha schematic view for describing conditions of peeling the processingfilm 100 from the substrate W.

As shown in FIG. 10A, the processing film 100 holds a removal object 103adhering to the surface layer 150 of the substrate W. The processingfilm 100 has a high solubility solid 110 (high solubility component in asolid state) and a low solubility solid 111 (low solubility component ina solid state). The high solubility solid 110 and the low solubilitysolid 111 are formed by at least a partial evaporation of a solventcontained in the processing liquid.

The high solubility solid 110 and the low solubility solid 111 arepresent in the processing film 100 in a mixed state. Strictly speaking,the processing film 100 is not in a state that the high solubilitysolids 110 and the low solubility solids 111 are uniformly distributedall over on the processing film 100. The processing film 100 has aportion in which the high solubility solids 110 are unevenly distributedand a portion in which the low solubility solids 111 are unevenlydistributed.

With reference to FIG. 10B, the high solubility solid 110 is dissolvedby the first peeling liquid. That is, the processing film 100 ispartially dissolved (dissolving step, partially dissolving step). Thehigh solubility solid 110 is dissolved, by which a penetrating hole 102is formed at a portion in which the high solubility solid 110 isunevenly distributed in the processing film 100 (penetrating holeforming step).

The penetrating hole 102 is particularly likely to be formed at aportion in which the high solubility solid 110 extends in a thicknessdirection T of the processing film 100. The penetrating hole 102 has asize of, for example, several nm in diameter in plan view. Thepenetrating hole 102 is a space which is formed in the processing film100 by dissolution of the high solubility solid 110.

Here, where the solvent remains appropriately in the processing film100, the first peeling liquid partially dissolves the processing film100 by being dissolved in the solvent remaining on the processing film100. In detail, the peeling liquid dissolves the high solubility solid110 in the processing film 100 to form the penetrating hole 102 by beingdissolved in the solvent remaining in the high solubility solid 110.Therefore, the first peeling liquid easily enters the processing film100 (dissolution entry step).

The first peeling liquid passes through the penetrating hole 102,reaches an interface between the processing film 100 and the substrate Wand acts on the interface. Action of the first peeling liquid on theinterface between the processing film 100 and the substrate W means thatthe first peeling liquid slightly dissolves a portion in contact withthe substrate W to peel the processing film 100 from the substrate W.

The low solubility component is low in solubility in the first peelingliquid, and the low solubility solid 111 is hardly dissolved by thefirst peeling liquid. Therefore, the low solubility solid 111 isslightly dissolved only near the surface thereof by the first peelingliquid. Therefore, the first peeling liquid which has reached near theupper surface of the substrate W via the penetrating hole 102 slightlydissolves a portion of the low solubility solid 111 near the uppersurface of the substrate W. Thereby, as shown in an enlarged view ofFIG. 10B, the first peeling liquid enters a space G1 between theprocessing film 100 and the upper surface of the substrate W, whilegradually dissolving the low solubility solid 111 near the upper surfaceof the substrate W (peeling liquid entry step).

Then, for example, with a peripheral edge of the penetrating hole 102 asa starting point, the processing film 100 becomes split into filmfragments 105. As shown in FIG. 100 , the film fragments 105 of theprocessing film 100 are peeled from the substrate W in a state ofholding the removal object 103 (processing film splitting step,processing film peeling step).

Then, the supply of the first peeling liquid is continued, and theprocessing film 100 made into the film fragments 105 is, thus, washedaway by the first peeling liquid in a state of holding the removalobject 103. In other words, the film fragments 105 which hold theremoval object 103 are pushed outside the substrate W and removed fromthe upper surface of the substrate W (processing film removing step,removal object removing step). Thereby, it is possible to satisfactorilyclean the upper surface of the substrate W.

Summary of First Preferred Embodiment

The strength of the peeling action (peeling force) by which the firstpeeling liquid peels the processing film 100 from the substrate W variesdepending on surface conditions of the upper surface of the substrate W.Specifically, the higher the hydrophilicity of the upper surface of thesubstrate W, the more easily the processing film 100 is peeled off bythe first peeling liquid. More specifically, the higher thehydrophilicity of the upper surface of the substrate W, the higher thewettability (affinity) of the peeling liquid for the substrate W, andthe first peeling liquid easily enters between the substrate W and theprocessing film 100. That is, the higher the hydrophilicity of the uppersurface of the substrate W, the more easily the processing film 100 ispeeled from the upper surface of the substrate W.

According to the present preferred embodiment, the processing film 100is formed on the hydrophilized upper surface of the substrate W and theprocessing film 100 is peeled off by the first peeling liquid.Therefore, it is possible to effectively peel the processing film 100from the substrate W.

Upon peeling of the processing film 100, the penetrating hole 102 isformed in the processing film 100 by the first peeling liquid.Therefore, the first peeling liquid reaches an interface between theprocessing film 100 and the substrate W via the penetrating hole 102.Thereby, the first peeling liquid enters between a portion of theprocessing film 100 which surrounds the penetrating hole 102 and theupper surface of the substrate W. Therefore, in comparison to anconfiguration in which the peeling liquid infiltrates into theprocessing film 100 and reaches an interface between the processing film100 and the substrate W, with no penetrating hole 102 formed in theprocessing film 100, the first peeling liquid acts quickly on theinterface between the processing film 100 and the substrate W. Althoughthe processing film 100 is partially dissolved by the first peelingliquid for formation of the penetrating hole 102, a remaining portionthereof is kept in a solid state. Therefore, the processing film 100 ina state of holding the removal object 103 can be effectively peeled fromthe upper surface of the substrate W.

In this way, while the first peeling liquid acts quickly on theinterface between the processing film 100 and the substrate W, a largeportion of the processing film 100 can be kept in a solid state.Therefore, the processing film 100 in a state of holding the removalobject 103 can be effectively peeled from the substrate W.

According to the present preferred embodiment, the solubility of thehigh solubility component to the first peeling liquid is higher thanthat of the low solubility component to the first peeling liquid.Therefore, the high solubility solid 110 is more easily dissolved in thefirst peeling liquid than the low solubility solid 111.

Therefore, the first peeling liquid is supplied to the upper surface ofthe substrate W to dissolve the high solubility solid 110 in the firstpeeling liquid, thereby forming the penetrating hole 102 in theprocessing film 100. On the other hand, the low solubility solid 111 isnot dissolved in the first peeling liquid but kept in a solid state.

Therefore, while the high solubility solid 110 is dissolved in the firstpeeling liquid, the low solubility solid 111 is not dissolved in thefirst peeling liquid but can be kept in a solid state. Accordingly, thefirst peeling liquid passes through the penetrating hole 102 formed bydissolution of the high solubility solid 110 and reaches the interfacebetween the substrate W and the low solubility solid 111.

Therefore, while the removal object 103 is held by the low solubilitysolid 111, the first peeling liquid acts on the interface between thelow solubility solid 111 and the substrate W. As a result, while theprocessing film 100 is quickly peeled from the substrate W, the removalobject 103 can be removed efficiently from the substrate W together withthe processing film 100.

Further, according to the present preferred embodiment, while the lowsolubility solid 111 contained in the processing film 100 is slightlydissolved in the first peeling liquid, the first peeling liquideffectively enters between the substrate W and the processing film 100.Therefore, the processing film 100 can be effectively peeled.

According to the present preferred embodiment, the first hydrophilizingliquid is supplied to the upper surface of the substrate W tohydrophilize the upper surface of the substrate W. The firsthydrophilizing liquid is supplied to the upper surface of the substrateW, by which the first hydrophilizing liquid spreads on the upper surfaceof the substrate W and the first hydrophilizing liquid can spread overthe entire upper surface of the substrate W. Thus, it is possible touniformly hydrophilize the entire upper surface of the substrate W.Since the entire upper surface of the substrate W is hydrophilized, inthe subsequent peeling step, the first peeling liquid easily acts on theinterface between the processing film 100 and the substrate W on theentire upper surface of the substrate W. Therefore, the processing film100 can be peeled uniformly from the entire upper surface of thesubstrate W.

According to the present preferred embodiment, the upper surface of thesubstrate W is hydrophilized so that the contact angle of pure water forthe upper surface of the substrate W can be smaller than 41.7°.Therefore, the first peeling liquid fully acts on the interface betweenthe substrate W and the processing film 100. Thereby, it is possible toeffectively peel the processing film 100 in a state of holding theremoval object 103 from the substrate W.

According to the present preferred embodiment, the contact angle of purewater for the processing film 100 is larger than 52° and smaller than61°. If the contact angle of pure water for the processing film 100 iswithin this range, the affinity of the first peeling liquid for theprocessing film 100 is sufficiently high. Thus, the peeling liquidsufficiently enters between the substrate W and the processing film 100,thereby effectively peeling the processing film 100 from the substrateW.

According to the present preferred embodiment, at least any one of Si,SiN, SiO₂, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru and amorphous carbon isexposed from the upper surface of the substrate W and, therefore, theupper surface of the substrate W can be hydrophilized by thehydrophilization step. For example, where the surface layer 150 of thesubstrate W includes a TiN layer (barrier layer 153) and an oxidizingliquid is used as the first hydrophilizing liquid, the oxide film 171 isformed on a surface of the TiN layer, thus making it possible tohydrophilize the upper surface of the substrate W. In this way, theupper surface of the substrate W is hydrophilized in advance, and theprocessing film 100 can thereby be effectively peeled from the substrateW.

Another Example of Substrate Processing According to First PreferredEmbodiment

FIG. 11 is a flowchart for describing another example of substrateprocessing by the substrate processing apparatus 1. The substrateprocessing shown in FIG. 11 is different from the substrate processingshown in FIG. 8 in that the first rinsing step (Step S3) and thereplacing step (Step S4) are omitted. If the first hydrophilizing liquidused in the hydrophilization step is a liquid having compatibility withthe processing liquid, as shown in FIG. 11 , the first rinsing step(Step S3) and the replacing step (Step S4) can be omitted. The firsthydrophilizing liquid is preferably the same liquid as the solventcontained in the processing liquid. The same liquid means that it iscomposed of the same substance. As an example of the firsthydrophilizing liquid having compatibility with the processing liquid,the organic solvent such as IPA is cited.

<Experiment of Peeling Processing Film>

Hereinafter, a description will be given of results of an experiment ofpeeling the processing film which was carried out for examining arelationship between a contact angle of pure water for a substrate andwhether the processing film is peeled. FIG. 12A is a schematic viewwhich describes procedures for measuring the contact angle of pure waterfor a surface an experimental substrate 200. FIG. 12B is a schematicview which describes procedures for peeling a processing film from theexperimental substrate 200.

In this experiment, as the experimental substrate 200, a substrate inwhich any one of Si (bare silicon: Bare-Si), SiN, SiO₂, W, TiN, Co, Cu,Ru and amorphous carbon (a-C) is exposed from the surface was used, andas the hydrophilizing liquid, any one of hydrochloric acid, SC1,hydrofluoric acid, SPM and IPA was used.

The experimental substrate 200 used in this experiment is a smallsubstrate in a square shape with the length of a side of 3 cm in planview.

Hydrogen chloride of hydrochloric acid used in this experiment is 0.4%in mass percent concentration. SC1 used in this experiment is a liquidmixture of ammonia water with 0.4% of a mass percent concentration ofammonia, and a hydrogen peroxide solution with 3.5% of a mass percentconcentration of hydrogen peroxide.

Hydrogen fluoride of hydrofluoric acid used in this experiment is 0.5%in mass percent concentration. SPM used in this experiment is a liquidmixture of heated dilute sulfuric acid with 64.0% of a mass percentconcentration of sulfuric acid, and a hydrogen peroxide solution with10.0% of a mass percent concentration of hydrogen peroxide. Pure waterused in this experiment is DIW.

The experiment was carried out by various combinations of the substrateand the hydrophilizing liquid.

In order to measure the contact angle of pure water for the experimentalsubstrate 200, as shown in FIG. 12A, the experimental substrate 200 wasimmersed in a hydrophilizing liquid. Thereafter, although not shown, DIWwas used to clean the experimental substrate 200 to remove thehydrophilizing liquid from the experimental substrate 200. A droplet 202of pure water (DIW) was formed on the hydrophilized experimentalsubstrate 200 to measure a contact angle θ1 of the droplet 202.

Then, in order to examine whether a processing film 201 is peeled fromthe experimental substrate 200, as shown in FIG. 12B, an unprocessedexperimental substrate 200 was immersed into the hydrophilizing liquid.Thereafter, although not shown, the experimental substrate 200 wascleaned with pure water and/or IPA, whenever necessary. After that,while a processing liquid was supplied to the experimental substrate200, the experimental substrate 200 was rotated at 10 rpm for about 2seconds and, thereafter, the experimental substrate 200 was rotated at1500 rpm for seconds to form a processing film 201. While theexperimental substrate 200 in which the processing film 201 was formedwas rotated at 800 rpm, a peeling liquid was supplied to theexperimental substrate 200. An observation was made for the surface ofthe experimental substrate 200 both before the supply of the processingliquid and after the supply of the peeling liquid for whether theprocessing film was peeled. As the peeling liquid, ammonia water with0.4% of a mass percent concentration was used.

The processing liquid used in the experiment of peeling the processingfilm contains, as a solute, at least one type of a low solubilitycomponent selected from the low solubility components which will bedescribed later and at least one type of a high solubility componentselected from the high solubility components which will be describedlater. The processing liquid used in the experiment of peeling theprocessing film is a processing liquid PL4 used in an experiment ofmeasuring a contact angle which will be described later by referring toFIG. 14 and FIG. 15 .

FIG. 13 is a table which shows the contact angle of pure water for thesurface of the experimental substrate 200 and whether the processingfilm 201 is peeled off by use of the peeling liquid. FIG. 13 is a tablefor summarizing the results of the experiment of peeling the processingfilm.

The table of FIG. 13 shows columns of “surface of substrate,”“hydrophilizing liquid,” “contact angle)(° of pure water” and “peelingof processing film.”

A name of a substance exposed from the surface of experimental substrate200 is given in each line of “surface of substrate.” A name of asubstance of the hydrophilizing liquid used in hydrophilizing theexperimental substrate 200 is given in each line of “hydrophilizingliquid.” A line which shows “−” in “hydrophilizing liquid” means thatthe experiment of peeling the processing film was given to a substratewhich was not hydrophilized. In each line of “contact angle (°) of purewater,” a contact angle θ1 of pure water for the experimental substrate200 which was hydrophilized by using the hydrophilizing liquid given onthe same line is described.

In each line of “peeling of the processing film,” whether the processingfilm 201 was peeled off by the peeling liquid from the experimentalsubstrate 200 hydrophilized by using the hydrophilizing liquid given inthe same line is described. “OK” means that the processing film 201 wassufficiently peeled and “NG” means that the processing film 201 wasinsufficiently peeled.

For example, in the table of FIG. 13 , the first line shows that thecontact angle θ1 of pure water for the experimental substrate 200 was4.8° after the experimental substrate 200 with SiN exposed to thesurface was hydrophilized with HCl, and the processing film 201 wassufficiently peeled from the experimental substrate 200 by the peelingliquid.

As shown in FIG. 13 , where the contact angle θ1 of pure water is notless than 41.7°, the processing film 201 was not sufficiently peeled.

As shown in FIG. 13 , even if the substance exposed from the surface ofthe experimental substrate 200 is the same, a difference inhydrophilizing liquid will result in a difference in contact angle θ1 ofpure water for the surface of the experimental substrate 200. Forexample, where HF was used as the hydrophilizing liquid to hydrophilizethe experimental substrate 200 in which TiN was exposed from thesurface, the contact angle θ1 of pure water was 15.2° and the processingfilm 201 was sufficiently removed. Where SC1 was used as thehydrophilizing liquid to hydrophilize the experimental substrate 200 inwhich TiN was exposed from the surface, the contact angle θ1 of purewater was 28.3° and the processing film 201 was sufficiently removed. Onthe other hand, where IPA was used as the hydrophilizing liquid tohydrophilize the experimental substrate 200 in which TiN was exposedfrom the surface, the contact angle θ1 of pure water was 41.7° and theprocessing film 201 was removed insufficiently.

Therefore, it is presumed that the use of an oxidizing liquid as thehydrophilizing liquid enhances further the hydrophilicity of the surfaceof the substrate than the use of an organic solvent as thehydrophilizing liquid. As reasons thereof, the following are cited.

Where an organic solvent is used as the hydrophilizing liquid, ahydrophobic organic substance adhering to the surface of the substrateis dissolved in the organic solvent to hydrophilize the surface of thesubstrate. Depending on the type, etc., of the organic substanceadhering to the surface of the substrate, there are some organicsubstances that are not dissolved in the organic solvent. Therefore, notall organic substances may be removed.

On the other hand, where an oxidizing liquid is used as thehydrophilizing liquid, a portion of the substrate near the surfacethereof is oxidized to form an oxide film on the surface of thesubstrate. Therefore, regardless of the type etc., of the organicsubstance adhering to the surface of the substrate, it is possible toefficiently enhance the hydrophilicity of the surface of the substrate.

It is noted that where no hydrophilization was carried out, the contactangle of pure water for the experimental substrate 200 in which TiN wasexposed from the surface was 59.6°. Therefore, even where any one ofIPA, HF and SC1 was used as the hydrophilizing liquid, the experimentalsubstrate 200 in which TiN was exposed from the surface washydrophilized.

<Experiment of Measuring Contact Angle for Processing Film>

Next, a description will be given of results of an experiment ofmeasuring a contact angle in which the contact angle of pure water for aprocessing film formed on a surface of an experimental substrate wasmeasured. FIG. is a schematic view which describes procedures formeasuring the contact angle of pure water for the surface of theprocessing film.

In this experiment, a substrate in which Si (bare silicon: Bare-Si) wasexposed from the surface was used as an experimental substrate 203, andIPA was used as a hydrophilizing liquid. Four types of processingliquids PL1˜PL4 were used as a processing liquid. Each of the processingliquids PL1˜PL4 contains IPA as a solvent. Each of the processingliquids PL1˜PL4 contains, as a solute, at least one type of a lowsolubility component selected from the low solubility components whichwill be described later and at least one type of a high solubilitycomponent selected from the high solubility components which will bedescribed later. The low solubility components contained in theprocessing liquids PL1˜PL4 are common. The high solubility componentscontained in the processing liquids PL1˜PL4 are substances which aredifferent from each other.

As shown in FIG. 15 , the experimental substrate 203 was immersed in IPAas a hydrophilizing liquid. Then, although not shown, DIW was used toclean the experimental substrate 203. Thereafter, a processing liquidwas dropped onto the surface of the experimental substrate 203.Thereafter, a solvent in the processing liquid was evaporated to form aprocessing film 204 on the surface of the experimental substrate 203.After that, a droplet 205 of pure water (DIW) was made on the processingfilm 204 formed in the experimental substrate 203 to measure a contactangle θ2 of the droplet 205.

FIG. 15 is a table which shows a contact angle θ2 of pure water for thesurface of the processing film 204 and whether the processing film 204is peeled off by a peeling liquid.

The table of FIG. 15 shows columns of “processing liquid” and “contactangle (°) of pure water.” In each line of “processing liquid,” each ofthe processing liquids PL1˜PL4 used for forming the processing film 204is described. In each line of “contact angle (°) of pure water,” thecontact angle θ2 of pure water for the processing film 204 formed byusing the processing liquid shown in the same line is described. Thecontact angle θ2 of pure water for the processing film 204 was an anglewithin a range of not less than 52° and not more than 61°. Therefore, itis presumed that the processing film formed in the hydrophilizedsubstrate can be effectively peeled off by the peeling liquid if thecontact angle θ2 of pure water for the processing film 204 is within therange.

Configuration of Substrate Processing Apparatus According to SecondPreferred Embodiment

FIG. 16 is a schematic view which describes an configuration example ofa processing unit 2 of a substrate processing apparatus 1P according toa second preferred embodiment. In FIG. 16 , the same configuration asthat shown in FIG. 1 ˜FIG. 15 which has been described previously willbe given the same reference numeral as that of FIG. 1 , etc., with adescription thereof omitted. In FIG. 17 ˜FIG. 21 which will be describedlater as well, the same reference numeral as that appeared in FIG. 1 ,etc., will be given, with a description thereof omitted.

The substrate processing apparatus 1P according to the second preferredembodiment is different from the substrate processing apparatus 1according to the first preferred embodiment mainly in that a peelingliquid discharged from a third moving nozzle 11 is a second peelingliquid such as diluted IPA on an upper surface of a substrate W and asurface of the substrate W can be hydrophilized by the second peelingliquid. Therefore, a first moving nozzle 9 for discharging ahydrophilizing liquid is not provided.

A processing film is more easily dissolved in an organic solvent than analkaline aqueous solution (alkaline liquid) such as ammonia water, purewater and an aqueous solution (non-alkaline aqueous solution) which isneutral or acidic. Individual components (solvent, low solubilitycomponent, high solubility component and corrosion preventive component)contained in a processing liquid are the same as those of theabove-described first preferred embodiment, and the details thereof willbe described later.

As the second peeling liquid, a liquid which is more likely to dissolvethe high solubility component contained in the processing liquid thanthe low solubility component contained in the processing liquid is used.The second peeling liquid is, for example, a diluted organic solventsuch as diluted IPA. The diluted organic solvent is an organic solventthat is diluted with pure water or a liquid mixture of an organicsolvent and pure water. In the present preferred embodiment, DIW is usedas pure water.

Where the second peeling liquid is diluted IPA, a mass percentconcentration of IPA in the second peeling liquid is preferably not lessthan 1% and not more than 33%, more preferably not less than 12% and notmore than 33%, and even more preferably not less than 20% and not morethan 33%.

If the mass percent concentration of IPA in the second peeling liquid isnot less than 1% and not more than 33%, the processing film can bepeeled from the substrate W, while the processing film on the substrateW is dissolved appropriately.

The second peeling liquid is a liquid capable of hydrophilizing(enhancing the hydrophilicity of) the upper surface of the substrate W.

If the mass percent concentration of IPA in diluted IPA is not less than12%, a contact angle of diluted IPA for the surface of the substrate Wis smaller than 41.7°. If the mass percent concentration of IPA indiluted IPA is not less than 12%, the surface of the substrate W can beappropriately hydrophilized.

Next, a description will be given of conditions in which the surface ofthe substrate W is hydrophilized. FIG. 17 is a schematic view fordescribing conditions in which the surface of the substrate W ishydrophilized by the second peeling liquid. Where a diluted organicsolvent such as diluted IPA is used as the second peeling liquid, asshown in FIG. 17 , a hydrophobic organic substance 170 present on thesurface of the substrate W is dissolved by the second peeling liquid tohydrophilize the surface of the substrate W. Where an organic substance170A less likely to be dissolved in the diluted organic solvent ispresent on the surface of the substrate W, the organic substance 170Aremains on the substrate W even after hydrophilization of the surface ofthe substrate W.

An organic substance is a part of a removal object present on thesurface of the substrate W. Even if the organic substance is removed byan organic solvent, the removal object cannot be removed sufficiently.Therefore, even where the surface of the substrate W is hydrophilized bythe diluted organic solvent, it is necessary to remove the removalobject by peeling of a processing film.

The substrate W having a surface from which at least any one of Si, SiN,SiO₂, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru and a-C is exposed can behydrophilized by the second peeling liquid. In particular, the substrateW having a surface from which at least any one of Si, SiN, SiO₂, W, TiN,Co, Cu, Ru and a-C is exposed is easily hydrophilized by the secondpeeling liquid, and the substrate W having a surface from which at leastany one of Si, SiN, SiO₂, W, TiN, Co and Cu is exposed is more likely tobe hydrophilized by the second peeling liquid.

If the contact angle of pure water for the processing film is largerthan 52° and smaller than 61°, a second peeling liquid which will bedescribed later sufficiently acts on an interface between the substrateW and the processing film. The use of the processing liquid makes itpossible to form a processing film in which the contact angle of purewater is larger than 52° and smaller than 61°.

The organic solvent discharged from the central nozzle 12 is an organicsolvent which is composed of the same substance (organic compound) asthe organic solvent in the diluted organic solvent as a second peelingliquid. Therefore, the organic solvent has compatibility with the secondpeeling liquid. The organic solvent dissolves and removes a residue ofthe processing liquid, which remains on the upper surface of thesubstrate W after the processing film is peeled and removed from theupper surface of the substrate W by the second peeling liquid. Theorganic solvent functions as a residue removing liquid. The residueremoving liquid is also referred to as a residue dissolving liquid. Theproperties of the residue removing liquid are as per the abovedescription. As the organic solvent discharged from the central nozzle12, there can be used, for example, organic solvents which are cited asthe organic solvents discharged from the central nozzle 12 in the firstpreferred embodiment. In the present preferred embodiment, the secondpeeling liquid discharged from the lower surface nozzle 13 is the sameas the second peeling liquid discharged from the third moving nozzle 11and, therefore, a description thereof will be omitted.

Substrate Processing According to Second Preferred Embodiment

FIG. 18 is a flowchart for describing an example of substrate processingby the substrate processing apparatus 1P. FIG. 18 shows processing whichis realized mainly by the controller 3 which executes programs. FIG.19A˜FIG. 19F are each a schematic view for describing conditions of eachstep of the substrate processing.

In the substrate processing by the substrate processing apparatus 1P,for example, as shown in FIG. 18 , a substrate carry-in step (Step S21),a processing liquid supplying step (Step S22), a processing film formingstep (Step S23), a peeling liquid supplying step (Step S24), a rinsingstep (Step S25), a residue removing liquid supplying step (Step S26), aspin drying step (Step S27) and a substrate carry-out step (Step S28)are executed in this order.

Hereinafter, a reference is mainly made to FIG. 16 and FIG. 18 . Areference is made to FIG. 19A˜FIG. 19F, whenever necessary.

First, an unprocessed substrate W is carried in a processing unit 2 froma carrier C by transfer robots IR, CR (refer to FIG. 1 ) and transferredto a spin chuck 5 (Step S1). Thereby, the substrate W is kepthorizontally by the spin chuck 5 (substrate holding step). When thesubstrate W is carried in, a facing member 6 retracts to an upperposition.

Holding of the substrate W by the spin chuck 5 is continued until thespin drying step (Step S27) ends. During a period of time from the startof the substrate holding step to the end of the spin drying step (StepS27), a guard raising/lowering unit 74 adjusts a height position of afirst guard 71A and that of a second guard 71B so that at least one ofguards 71 may be positioned at an upper position.

In a state that the substrate W is held by the spin chuck 5, a spinmotor 23 rotates a spin base 21. Thereby, the rotation of the substrateW held horizontally is started (substrate rotating step). A facingmember rotating unit 62 may rotate the facing member 6 synchronouslywith the spin base 21. Synchronous rotation is to rotate the facingmember 6 in the same direction and at the same rotational speed as thespin base 21.

Next, the processing liquid supplying step (Step S22) in which, afterthe transfer robot CR has been retracted outside the processing unit 2,a processing liquid is supplied to the upper surface of the substrate Wis executed. Specifically, in a state that the facing member 6 ispositioned at the retract position, a second nozzle moving unit 36 movesa second moving nozzle 10 to a processing position. The processingposition of the second moving nozzle 10 is, for example, a centralposition. When the facing member 6 is positioned at the retractposition, each of moving nozzles moves horizontally between the facingmember 6 and the substrate W. The retract position may be an upperposition.

In a state that the second moving nozzle 10 is at the processingposition, a processing liquid valve 54 is opened. Thereby, as shown inFIG. 19A, a processing liquid is supplied (discharged) from the secondmoving nozzle 10 toward the central region of the upper surface of thesubstrate W in the rotating state (processing liquid supplying step,processing liquid discharging step). The processing liquid supplied tothe upper surface of the substrate W spreads over the entire substrate Wby a centrifugal force. Thereby, a liquid film 101 of the processingliquid (processing liquid film) is formed on the substrate W (processingliquid film forming step).

The supply of the processing liquid from the second moving nozzle 10 iscontinued for a predetermined time of, for example, 2 seconds˜4 seconds.In the processing liquid supplying step, the substrate W is rotated at apredetermined processing liquid rotational speed of, for example, 10rpm˜1500 rpm.

Next, the processing film forming step (Step S23) shown in FIG. 19B andFIG. 19C is executed. In the processing film forming step, theprocessing liquid on the substrate W is solidified or cured to form, onthe upper surface of the substrate W, a processing film 100 which holdsa removal object present on the substrate W (refer to FIG. 19C).

In the processing film forming step, first, a processing liquid filmthinning step (processing liquid spin off step) in which the liquid film101 of the processing liquid on the substrate W is made thin inthickness is executed. Specifically, the processing liquid valve 54 isclosed. Thereby, as shown in FIG. 19B, the supply of the processingliquid to the substrate W is stopped. Then, the second nozzle movingunit 36 moves the second moving nozzle 10 to a home position.

As shown in FIG. 19B, in the processing liquid film thinning step, thesubstrate W is rotated in a state that the supply of the processingliquid to the upper surface of the substrate W is stopped and,therefore, the processing liquid is partially removed from the uppersurface of the substrate W. The liquid film 101 on the substrate W is,thereby, made appropriate in thickness. Even after movement of thesecond moving nozzle 10 to the home position, the facing member 6 iskept at the retract position.

In the processing liquid film thinning step, the spin motor 23 changes arotational speed of the substrate W to a predetermined processing liquidfilm thinning speed. The processing liquid film thinning speed is, forexample, 300 rpm˜1500 rpm. The rotational speed of the substrate W maybe kept fixed within a range of 300 rpm˜1500 rpm or may be changedwithin a range of 300 rpm˜1500 rpm whenever necessary during theprocessing liquid film thinning step. The processing liquid filmthinning step is executed for a predetermined time of, for example, 30seconds.

In the processing film forming step, a processing liquid solventevaporation step in which, after the processing liquid film thinningstep, a solvent is partially evaporated (volatilized) from the liquidfilm 101 of the processing liquid is executed. In the processing liquidsolvent evaporation step, the liquid film 101 on the substrate W isheated for partially evaporating the solvent of the processing liquid onthe substrate W.

Specifically, as shown in FIG. 19C, the facing member raising/loweringunit 61 moves the facing member 6 to a proximity position. The proximityposition may be a lower position. The proximity position is a positionin which a distance from the upper surface of the substrate W to thefacing surface 6 a is, for example, 1 mm.

Next, the gas valve 53 is opened. Thereby, a gas is supplied to a spacebetween the upper surface of the substrate W (the upper surface of theliquid film 101) and the facing surface 6 a of the facing member 6 (gassupplying step).

Evaporation (volatilization) of the solvent in the liquid film 101 ispromoted by the gas being blown onto the liquid film 101 on thesubstrate W (processing liquid solvent evaporation step, processingliquid solvent evaporation promoting step). Therefore, it is possible toshorten a time necessary for forming the processing film 100. In theprocessing film forming step, the central nozzle 12 functions as anevaporation unit (evaporation promoting unit) for evaporating thesolvent in the processing liquid.

Even after removal of a portion of the processing liquid from thesubstrate W by the processing liquid film thinning step of the liquidfilm 101, the rotation of the facing member 6 and the substrate W iscontinued. Therefore, a centrifugal force resulting from the rotation ofthe facing member 6 and the substrate W acts on a gas which isdischarged from the central nozzle 12. Due to action of the centrifugalforce, a gas stream in which the gas moves from a central side of thesubstrate W to a peripheral edge side thereof is formed. Therefore,elimination of a gaseous solvent in contact with the liquid film 101from a space between the facing member 6 and the substrate W ispromoted. Thereby, evaporation of the solvent in the liquid film 101 ispromoted. In this way, the facing member 6 and the spin motor 23function as an evaporation unit (evaporation promoting unit) forevaporating (volatilizing) the solvent in the processing liquid. Onlythe substrate W may be rotated, with the facing member 6 not beingrotated.

Also, the heating medium valve 88 is opened. Thereby, as shown in FIG.19C, a heating medium is supplied (discharged) from the lower surfacenozzle 13 toward the central region of the lower surface of thesubstrate W in the rotating state (heating medium supplying step,heating medium discharging step). The heating medium supplied from thelower surface nozzle 13 to the lower surface of the substrate W spreadsradially by receiving a centrifugal force and spreads over the entirelower surface of the substrate W.

The supply of the heating medium to the substrate W is continued for apredetermined time of, for example, 60 seconds. In the processing liquidsolvent evaporation step, the substrate W is rotated at a predeterminedevaporation rotational speed of, for example, 1000 rpm.

By the supply of the heating medium to the lower surface of thesubstrate W, the liquid film 101 on the substrate W is heated via thesubstrate W. The evaporation (volatilization) of the solvent in theliquid film 101 is, thereby, promoted (processing liquid solventevaporation step, processing liquid solvent evaporation promoting step).Thus, it is possible to shorten a time necessary for forming theprocessing film 100. In the processing film forming step as well, thelower surface nozzle 13 functions as an evaporation unit (evaporationpromoting unit) for evaporating (volatilizing) the solvent in theprocessing liquid.

By execution of the processing liquid film thinning step and theprocessing liquid solvent evaporation step, the processing liquid issolidified or cured. Thereby, a processing film 100 which holds aremoval object is formed on the entire upper surface of the substrate W.

In this way, the substrate rotating unit (spin motor 23), the facingmember rotating unit 62, the central nozzle 12 and the lower surfacenozzle 13 form a processing film forming unit in which the processingliquid is solidified or cured to form the processing film 100 in a solidstate.

Gas blowing, rotation of the substrate W and heating of the substrate Wcan be used to quickly form the processing film 100. However, it is alsopossible to form the processing film 100 by the gas blowing and rotationof the substrate W. In other words, heating by a heating medium is notalways necessary in formation of the processing film 100. Therefore, thesupply of the heating medium to the substrate W may be omitted.

In the processing liquid solvent evaporation step, the substrate W ispreferably heated so that a temperature of the substrate W may be lessthan a boiling point of the solvent. The substrate W is heated up to thetemperature less than the boiling point of the solvent, by whichexcessive evaporation of the solvent can be suppressed and the solventremains appropriately in the processing film 100. Thus, in comparison toa case in which no solvent remains in the processing film 100, thesecond peeling liquid easily acts on the processing film 100 in thesubsequent peeling liquid supplying step (Step S24).

Next, the peeling liquid supplying step (Step S24) in which the secondpeeling liquid is supplied toward the upper surface of the substrate Wis executed. Specifically, the heating medium valve 88 is closed.Thereby, the supply of the heating medium to the lower surface of thesubstrate W is stopped. Also, the gas valve 53 is closed. The supply ofthe gas to a space between the facing surface 6 a of the facing member 6and the upper surface of the substrate W is thereby stopped.

Then, the facing member raising/lowering unit 61 moves the facing member6 to a retract position. In a state that the facing member 6 ispositioned at the retract position, the third nozzle moving unit 37moves the third moving nozzle 11 to a processing position. Theprocessing position of the third moving nozzle 11 is, for example, acentral position.

Then, in a state that the third moving nozzle 11 is positioned at theprocessing position, the upper peeling liquid valve 55 is opened.Thereby, as shown in FIG. 19D, the second peeling liquid is supplied(discharged) from the third moving nozzle 11 toward the central regionof the upper surface of the substrate W in the rotating state (upperpeeling liquid supplying step, upper peeling liquid discharging step).The peeling liquid supplied to the upper surface of the substrate Wspreads over the entire upper surface of the substrate W by acentrifugal force. Thereby, the processing film 100 on the upper surfaceof the substrate W is peeled and removed outside the substrate Wtogether with the second peeling liquid.

At the same time when the upper peeling liquid valve 55 is opened, thelower peeling liquid valve 87 is opened. Thereby, as shown in FIG. 19D,the second peeling liquid is supplied (discharged) from the lowersurface nozzle 13 toward the central region of the lower surface of thesubstrate W in the rotating state (lower peeling liquid supplying step,lower peeling liquid discharging step). The second peeling liquidsupplied to the lower surface of the substrate W spreads over the entirelower surface of the substrate W by a centrifugal force.

The supply of the second peeling liquid to the upper surface and thelower surface of the substrate W is continued for a predetermined timeof, for example, 60 seconds. In the peeling liquid supplying step, thesubstrate W is rotated at a predetermined peeling rotational speed of,for example, 800 rpm.

Here, there may be a possibility in which, in the processing liquidsupplying step (Step S22) shown in FIG. 19A, the processing liquidsupplied to the upper surface of the substrate W adheres to the lowersurface of the substrate W via a peripheral edge of the substrate W andthe processing liquid adhering to the lower surface of the substrate Wis solidified or cured to form a solid.

Even in this case, as shown in FIG. 19D, in the peeling liquid supplyingstep (Step S24), during a time when the second peeling liquid issupplied to the upper surface of the substrate W, the second peelingliquid is supplied (discharged) from the lower surface nozzle 13 to thelower surface of the substrate W. Therefore, even in a case in which asolid of the processing liquid is formed on the lower surface of thesubstrate W, the solid can be peeled from the lower surface of thesubstrate W and removed.

After the peeling liquid supplying step (Step S24), the rinsing step(Step S25) in which the second peeling liquid is washed away from thesubstrate W by a rinse liquid is executed. Since the second peelingliquid is expelled outside the substrate W by the rinse liquid, therinsing step (Step S25) is also referred to as a peeling liquidexpelling step.

Specifically, the upper peeling liquid valve 55 and the lower peelingliquid valve 87 are closed. Thereby, the supply of the second peelingliquid to the upper surface and the lower surface of the substrate W isstopped. Then, the third nozzle moving unit 37 moves the third movingnozzle 11 to the home position. Then, as shown in FIG. 19E, the facingmember raising/lowering unit 61 moves the facing member 6 to theprocessing position between the retract position and the lower position.When the facing member 6 is positioned at the processing position, adistance between the upper surface of the substrate W and the facingsurface 6 a is, for example, 30 mm.

Then, in a state that the facing member 6 is positioned at theprocessing position, the upper rinse liquid valve 51 is opened. Thereby,as shown in FIG. 19E, the rinse liquid is supplied (discharged) from thecentral nozzle 12 toward the central region of the upper surface of thesubstrate W in the rotating state (upper rinse liquid supplying step,upper rinse liquid discharging step). The rinse liquid supplied to theupper surface of the substrate W spreads over the entire upper surfaceof the substrate W by a centrifugal force. Thereby, the second peelingliquid adhering to the upper surface of the substrate W is expelledoutside the substrate W together with the rinse liquid and replaced withthe rinse liquid (peeling liquid expelling step).

Also, at the same time when the upper rinse liquid valve 51 is opened,the lower rinse liquid valve 86 is opened. Thereby, as shown in FIG.19E, the rinse liquid is supplied (discharged) from the lower surfacenozzle 13 toward the central region of the lower surface of thesubstrate W in the rotating state (lower rinse liquid supplying step,lower rinse liquid discharging step). Thereby, the second peeling liquidadhering to the lower surface of the substrate W is expelled outside thesubstrate W together with the rinse liquid and replaced with the rinseliquid (lower peeling liquid expelling step).

The supply of the rinse liquid to the upper surface and the lowersurface of the substrate W is continued for a predetermined time of, forexample, 30 seconds. In the rinsing step (Step S25), the substrate W isrotated at a predetermined peeling liquid removing rotational speed of,for example, 800 rpm.

Next, the residue removing liquid supplying step (Step S28) in which theresidue removing liquid such as IPA is supplied is executed.

Specifically, the upper rinse liquid valve 51 and the lower rinse liquidvalve 86 are closed. Thereby, the supply of the rinse liquid to theupper surface and the lower surface of the substrate W is stopped. Then,in a state that the facing member 6 is positioned at the processingposition, the organic solvent valve 52 is opened. Thereby, as shown inFIG. 19F, the residue removing liquid (organic solvent) is supplied(discharged) from the central nozzle 12 toward the central region of theupper surface of the substrate W in the rotating state (residue removingliquid supplying step, residue removing liquid discharging step).

The residue removing liquid supplied from the central nozzle 12 to theupper surface of the substrate W spreads radially by receiving acentrifugal force and spreads over the entire upper surface of thesubstrate W. There may be a case in which a residue of the processingfilm remains on the upper surface of the substrate W even after theprocessing film has been peeled from the substrate W by the secondpeeling liquid and removed outside the substrate W. The residue removingliquid supplied to the upper surface of the substrate W dissolves theresidue of the processing film. The residue removing liquid which hasdissolved the residue of the processing film is expelled from aperipheral edge of the upper surface of the substrate W by a centrifugalforce. Thereby, the residue of the processing film on the substrate W isremoved (residue removing step).

In the residue removing liquid supplying step, the discharge of theresidue removing liquid from the central nozzle 12 is continued for apredetermined time of, for example, 30 seconds. In the residue removingliquid supplying step, the substrate W is rotated at a predeterminedresidue removing rotational speed of, for example, 300 rpm.

Next, the spin drying step (Step S7) in which the substrate W is rotatedat a high speed to dry the upper surface of the substrate W is executed.Specifically, the organic solvent valve 52 is closed. Thereby, thesupply of the organic solvent to the upper surface of the substrate W isstopped. Then, the facing member raising/lowering unit 61 moves thefacing member 6 to a drying position lower than the processing position.When the facing member 6 is positioned at the drying position, adistance between the facing surface 6 a of the facing member 6 and theupper surface of the substrate W is, for example, 1.5 mm. Then, the gasvalve 53 is opened. Thereby, a gas is supplied to a space between theupper surface of the substrate W and the facing surface 6 a of thefacing member 6.

Then, the spin motor 23 accelerates the rotation of the substrate W torotate the substrate W at a high speed. The substrate W in the spindrying step is rotated at a drying speed of, for example, 1500 rpm. Thespin drying step is executed for a predetermined time of, for example,30 seconds. Thereby, a large centrifugal force acts on an organicsolvent on the substrate W and the organic solvent on the substrate W isspun off around the substrate W. In the spin drying step, a gas issupplied to a space between the upper surface of the substrate W and thefacing surface 6 a of the facing member 6, thereby promoting theevaporation of the organic solvent.

Then, the spin motor 23 stops the rotation of the substrate W. The guardraising/lowering unit 74 moves the first guard 71A and the second guard71B to the lower position. The gas valve 53 is closed. Then, the facingmember raising/lowering unit 61 moves the facing member 6 to an upperposition.

The transfer robot CR enters the processing unit 2, scoops up aprocessed substrate W from the chuck pin 20 of the spin chuck 5 andcarries it outside the processing unit 2 (Step S28). The substrate W istransferred from the transfer robot CR to the transfer robot IR andhoused in a carrier C by the transfer robot IR.

Conditions of Peeling of Processing Film in Second Preferred Embodiment

Next, conditions in which the processing film 100 is peeled from thesubstrate W will be described in detail with reference to FIG. 30A˜FIG.30C. FIG. 30A FIG. 30C are each a schematic view for describing theconditions in which the processing film 100 is peeled from the substrateW.

As shown in FIG. 30A, the processing film 100 holds a removal object 103which adhering to a surface layer 150 of the substrate W. The processingfilm 100 has a high solubility solid 110 (high solubility component in asolid state) and a low solubility solid 111 (low solubility component ina solid state). The high solubility solid 110 and the low solubilitysolid 111 are formed by evaporating at least a portion of a solventcontained in a processing liquid.

In the processing film 100, the high solubility solid 110 and the lowsolubility solid 111 are present in a mixed state. Strictly speaking,the processing film 100 is not in a state that the high solubilitysolids 110 and the low solubility solids 111 are uniformly distributedall over the processing film 100. The processing film 100 has a portionin which the high solubility solids 110 are unevenly distributed and aportion in which the low solubility solids 111 are unevenly distributed.

With reference to FIG. 30B, the high solubility solid 110 is dissolvedby a second peeling liquid. That is, the processing film 100 ispartially dissolved (dissolving step, partially dissolving step). Thehigh solubility solid 110 is dissolved, by which a penetrating hole 102is formed at a portion of the processing film 100 in which the highsolubility solids 110 are unevenly distributed (penetrating hole formingstep).

The penetrating hole 102 is particularly likely to be formed at aportion in which the high solubility solid 110 extends in a thicknessdirection T of the processing film 100. The penetrating hole 102 has asize of, for example, several nm in diameter in plan view.

Here, where a solvent remains appropriately in the processing film 100,the second peeling liquid dissolves partially the processing film 100,while being dissolved in the solvent remaining in the processing film100. In detail, while being dissolved in the solvent remaining in thehigh solubility solid 110, the second peeling liquid dissolves the highsolubility solid 110 in the processing film 100 to form the penetratinghole 102. Thus, the second peeling liquid easily enters the processingfilm 100 (dissolution entry step).

The second peeling liquid passes through the penetrating hole 102,reaches an upper surface of the substrate W and hydrophilizes the uppersurface of the substrate W (hydrophilization step). The upper surface ofthe substrate W is hydrophilized, and a contact angle of pure water forthe upper surface of the substrate W becomes smaller than 41.7° (contactangle reducing step). The second peeling liquid which has reached theupper surface of the substrate W acts on an interface between theprocessing film 100 and the substrate W, peels the processing film 100and removes the peeled processing film 100 from the upper surface of thesubstrate W (peeling removal step).

In detail, the low solubility component is low in solubility in thesecond peeling liquid and the low solubility solid 111 is hardlydissolved by the second peeling liquid. Therefore, the low solubilitysolid 111 is slightly dissolved by the second peeling liquid only nearthe surface thereof. Accordingly, the second peeling liquid which hasreached near the upper surface of the substrate W via the penetratinghole 102 slightly dissolves a portion of the low solubility solid 111near the upper surface of the substrate W. Thereby, as shown in anenlarged view of FIG. 30B, the second peeling liquid enters a gap G1between the processing film 100 and the upper surface of the substrateW, while gradually dissolving the low solubility solid 111 near theupper surface of the substrate W (peeling liquid entry step).

Then, for example, with a peripheral edge of the penetrating hole 102 asa starting point, the processing film 100 is split into film fragments105, and as shown in FIG. 100 , the film fragments 105 of the processingfilm 100 are peeled from the substrate W in a state of holding theremoval object 103 (processing film splitting step, processing filmpeeling step).

Then, by continuing the supply of the second peeling liquid, theprocessing film 100 that has become the film fragments 105 is washedaway by the second peeling liquid in a state of holding the removalobject 103. In other words, the film fragments 105 which hold theremoval object 103 are pushed outside the substrate W and removed fromthe upper surface of the substrate W (processing film removal step,removal object removal step). Thereby, it is possible to satisfactorilyclean the upper surface of the substrate W.

Summary of Second Preferred Embodiment

As described above, according to the second preferred embodiment, theprocessing liquid supplied to the upper surface of the substrate W issolidified or cured, thereby, forming the processing film 100 whichholds the removal object 103. Thereafter, the second peeling liquid issupplied toward the upper surface of the substrate W. By the supply ofthe second peeling liquid, the penetrating hole 102 is formed in theprocessing film 100, the upper surface of the substrate W ishydrophilized, and the processing film 100 in a state of holding theremoval object 103 is peeled from the upper surface of the substrate W.In other words, the formation of the penetrating hole 102,hydrophilization of the substrate W and peeling of the processing film100 are realized by the supply of the second peeling liquid alone.

According to the second preferred embodiment, the second peeling liquidis a liquid mixture of an organic solvent and water. The processing film100 is more easily dissolved by an organic solvent than by water orammonia water. Therefore, the second peeling liquid which is a liquidmixture of an organic solvent and water is less likely to dissolve theprocessing film 100 than an organic solvent. Therefore, the processingfilm 100 is partially dissolved by the second peeling liquid. Thereby,the penetrating hole 102 (space) is formed in the processing film 100.The second peeling liquid passes through the penetrating hole 102 andreach the upper surface of the substrate W. The second peeling liquidwhich has reached the upper surface of the substrate W acts on aninterface between the processing film 100 and the substrate W.

Therefore, in comparison to a method in which, with no space such as thepenetrating hole 102 formed in the processing film 100, throughinfiltration of the peeling liquid into the processing film 100, thepeeling liquid reaches an interface between the processing film 100 andthe substrate W, a large amount of the second peeling liquid actsquickly to reach the interface between the processing film 100 and thesubstrate W.

The peeling liquid is a diluted organic solvent. The processing film 100is more easily dissolved by an organic solvent than by water or ammoniawater. Therefore, the diluted organic solvent is higher in solubility ofthe processing film 100 than water or ammonia water. Although theprocessing film 100 is partially dissolved by the second peeling liquidfor formation of the penetrating hole 102, a remaining portion thereofis kept in a solid state. Therefore, a surface of a portion of theprocessing film 100 which is kept in a solid state (the low solubilitysolid 111) is appropriately dissolved by the second peeling liquid, andthe processing film 100 in a state of holding the removal object 103 canbe effectively peeled from the upper surface of the substrate W.Therefore, in comparison to a method in which the processing film 100 ispeeled without using an organic solvent, the processing film 100 can beefficiently peeled.

According to the second preferred embodiment, the solubility of the highsolubility component to the second peeling liquid is higher than that ofthe low solubility component to the second peeling liquid. Therefore,the high solubility solid 110 is more easily dissolved in the secondpeeling liquid than the low solubility solid 111. Therefore, the highsolubility solid 110 is dissolved in the second peeling liquid to formthe penetrating hole 102 in the processing film 100. On the other hand,the low solubility solid 111 is not dissolved by the peeling liquid butkept in a solid state.

Therefore, while the high solubility solid 110 is being dissolved in thesecond peeling liquid, the low solubility solid 111 is not dissolved inthe peeling liquid but can be kept in a solid state. Thus, the secondpeeling liquid passes through the penetrating hole 102 formed bydissolution of the high solubility solid 110 and reaches an interfacebetween the substrate W and the low solubility solid 111. Therefore,with the removal object 103 held by the low solubility solid 111, thesecond peeling liquid acts on the interface between the low solubilitysolid 111 and the substrate W. As a result, while the processing film100 is quickly peeled from the substrate W, the removal object 103 canbe effectively removed from the substrate W together with the processingfilm 100.

According to the second preferred embodiment, the second peeling liquidenters between the upper surface of the substrate W and the processingfilm 100 (low solubility solid 111). Therefore, the second peelingliquid acts on an interface between the processing film 100 and thesubstrate W and the processing film 100 can be more efficiently peeledfrom the upper surface of the substrate W.

In the case of the second peeling liquid which is diluted IPA, if a masspercent concentration of IPA in the second peeling liquid is not lessthan 12% and not more than 33%, the surface of the processing film 100can be appropriately dissolved so that the processing film 100 in astate of holding the removal object 103 can be peeled from the uppersurface of the substrate W.

According to the second preferred embodiment, in the residue removingliquid supplying step (Step S28), the residue removing liquid suppliedto the upper surface and the lower surface of the substrate W is theorganic solvent which is composed of the same substance (IPA) as theorganic solvent in the second peeling liquid. That is, the organicsolvent in the diluted organic solvent used as the second peeling liquidis the same organic compound as the organic solvent used as the residueremoving liquid. Therefore, in comparison to a method in which theorganic solvent in the second peeling liquid is a substance (organiccompound) which is different from the organic solvent used as theresidue removing liquid, types of the liquid to be used can be reduced.Therefore, it is possible to reduce costs required for removing theremoval object 103 from the substrate W.

The higher the hydrophilicity of the upper surface of the substrate W,the more easily the peeling liquid acts on an interface between thesubstrate W and the processing film 100, and the processing film 100 canbe effectively peeled from the upper surface of the substrate W. In thesecond preferred embodiment, a site of the upper surface of thesubstrate W which is exposed by formation of the penetrating hole 102 ishydrophilized by the second peeling liquid. Therefore, the secondpeeling liquid effectively acts on an interface between a portion of theprocessing film 100 which surrounds the penetrating hole 102 and thesubstrate W. In other words, the second peeling liquid acts quickly toenter between the processing film 100 and the substrate W. Therefore, itis possible to effectively remove the processing film 100 in a state ofholding the removal object 103 from the upper surface of the substrateW.

In the second preferred embodiment, since the second peeling liquid is adiluted organic solvent and the residue removing liquid is an organicsolvent, the residue removing liquid is dissolved in the second peelingliquid. Therefore, in the substrate processing (refer to FIG. 18 ) ofthe second preferred embodiment, the rinsing step (Step S25) may beomitted.

Modified Example of Substrate Processing Apparatus According to SecondPreferred Embodiment

FIG. 21 is a schematic view for describing conditions of the peelingliquid supplying step (Step S24) of substrate processing by a modifiedexample of the substrate processing apparatus 1P according to the secondpreferred embodiment. In the substrate processing apparatus 1P of themodified example, a mixing valve 90 is connected to the upper peelingliquid piping 45 which supplies a second peeling liquid to the thirdmoving nozzle 11.

An organic solvent piping 91 and a pure water piping 92 are connected tothe mixing valve 90. An organic solvent valve 93A which is interposed inthe organic solvent piping 91 is opened, by which an organic solventsuch as IPA is supplied to the mixing valve 90. A pure water valve 94Awhich is interposed in the pure water piping 92 is opened, by which purewater such as DIW is supplied to the mixing valve 90. An opening degreeof an organic solvent adjusting valve 93B interposed in the organicsolvent piping 91 and an opening degree of a pure water adjusting valve94B interposed in the pure water piping 92 are adjusted, thus making itpossible to adjust a concentration of the organic solvent in the dilutedorganic solvent inside the mixing valve 90.

Therefore, in the peeling liquid supplying step (Step S24), duringsupplying the second peeling liquid to the upper surface of thesubstrate W, the concentration of the organic solvent in the secondpeeling liquid supplied to the upper surface of the substrate W can beadjusted by adjusting the opening degree of the organic solventadjusting valve 93B and that of the pure water adjusting valve 94B(organic solvent concentration adjusting step). For example, byincreasing the opening degree of the organic solvent adjusting valve93B, the organic solvent in the second peeling liquid can be increasedin concentration during the supply of the second peeling liquid to theupper surface of the substrate W.

The organic solvent is increased in concentration to make the secondpeeling liquid free of pure water, and thus making it possible to removea residue of the processing film 100 from the upper surface of thesubstrate W. That is, the organic solvent discharged from the thirdmoving nozzle 11 functions as a residue removing liquid. Thereby, it ispossible to smoothly start the residue removing liquid supplying stepafter the peeling liquid supplying step.

In contrast, a decrease in the opening degree of the organic solventadjusting valve 93B makes it possible to decrease the concentration ofthe organic solvent in the second peeling liquid during the supply ofthe second peeling liquid to the upper surface of the substrate W.

Configuration of Substrate Processing Apparatus According to ThirdPreferred Embodiment

FIG. 22 is a schematic partial sectional view which shows a generalconfiguration of a processing unit 2 provided in a substrate processingapparatus 1Q according to the third preferred embodiment of the presentinvention.

In FIG. 22 , the same configuration as the configuration shown in FIG. 1˜FIG. 21 which has been described previously will be given the samereference numeral as that of FIG. 1 , etc., with a description thereofomitted. Also, in FIG. 23 ˜FIG. 25D which will be described later, thesame reference numeral as that indicated in FIG. 1 , etc., will begiven, with a description thereof omitted.

The substrate processing apparatus 1Q according to the third preferredembodiment is different from the substrate processing apparatus 1P(refer to FIG. 16 ) according to the second preferred embodiment in thatthe processing unit 2 includes a fourth moving nozzle 14 which supplies(discharges) a dissolving liquid such as ammonia water toward an uppersurface of the substrate W which is held by a spin chuck 5. The fourthmoving nozzle 14 is an example of a dissolving liquid supplying unit.

When positioned at a center position, the fourth moving nozzle 14 facesa central region of the upper surface of the substrate W. Whenpositioned at a home position, the fourth moving nozzle 14 does not facethe upper surface of the substrate W but is positioned outside aprocessing space 7 in plan view. The fourth moving nozzle 14 moves closeto the upper surface of the substrate W and retracts upward from theupper surface of the substrate W by moving in a vertical direction.

A fourth nozzle moving unit 38 has the same configuration as the firstnozzle moving unit 35. That is, the fourth nozzle moving unit 38 mayinclude an arm (not shown) which is coupled to the fourth moving nozzle14 and extends horizontally, a turning shaft (not shown) which iscoupled to the arm and extends along the vertical direction and aturning shaft driving unit (not shown) which raises, lowers and turnsthe turning shaft.

The fourth moving nozzle 14 is connected to a dissolving liquid piping47 which guides a dissolving liquid to the fourth moving nozzle 14. Whena dissolving liquid valve 57 interposed in the dissolving liquid piping47 is opened, the dissolving liquid is continuously discharged downwardfrom a discharge port of the fourth moving nozzle 14. When the fourthmoving nozzle 14 is positioned at the central position and thedissolving liquid valve 57 is opened, the dissolving liquid is suppliedto a central region of the upper surface of the substrate W.

As the dissolving liquid, there can be used a liquid capable ofappropriately dissolving a processing film on the substrate W. Thedissolving liquid is a liquid which contains a substance different froma peeling liquid.

In detail, a liquid which is more likely to dissolve a high solubilitycomponent contained in a processing liquid rather than a low solubilitycomponent contained in the processing liquid as the dissolving liquid isused. The dissolving liquid is, for example, ammonia water with 0.4% ofa mass percent concentration.

The dissolving liquid may be, for example, an alkaline aqueous solution(alkaline liquid) other than ammonia water. As specific examples ofalkaline aqueous solutions other than ammonia water, cited are anaqueous solution of TMAH (tetramethylammonium hydroxide), a cholineaqueous solution and any combination of them. The dissolving liquid maybe pure water (preferably DIW) or may be an aqueous solution(non-alkaline aqueous solution) which is neutral or acidic.

The dissolving liquid is preferably alkaline. The dissolving liquid ispreferably 7˜13 in pH. In detail, the dissolving liquid is preferably8˜13 in pH and more preferably 10˜13 and even more preferably 11˜12.5.The pH is preferably measured after degassing for avoiding influence dueto dissolution of carbon dioxide in air.

A large portion of the solvent of the dissolving liquid is pure water. Apercentage of pure water contained in the solvent of the dissolvingliquid is 50˜100 mass % (preferably 70˜100 mass %, more preferably90˜100 mass %, even more preferably 95˜100 mass % and yet even morepreferably 99˜100 mass %). “Mass %” is a percentage of a mass of acertain component with respect to a total mass of a liquid. The soluteof the dissolving liquid is 0.1˜10% in mass percent concentration(preferably, 0.2˜8% and more preferably 0.3˜6%).

As shown in FIG. 5 , the dissolving liquid valve 57 and the fourthnozzle moving unit 38 are controlled by a controller 3.

Substrate Processing According to Third Preferred Embodiment

FIG. 23 is a flowchart for describing an example of substrate processingby the substrate processing apparatus 1Q according to the thirdpreferred embodiment. The substrate processing by the substrateprocessing apparatus 1Q is different from the substrate processing(refer to FIG. 18 ) by the substrate processing apparatus 1P accordingto the second preferred embodiment mainly in that, between theprocessing film forming step (Step S23) and the peeling liquid supplyingstep (Step S24), a dissolving liquid supplying step (Step S30) and arinsing step (Step S31) are executed in this order. Hereinafter, adescription will be given of the substrate processing by the substrateprocessing apparatus 1Q, with an emphasis placed on the dissolvingliquid supplying step (Step S30) and the rinsing step (Step S31).

It is noted that an configuration of the substrate W which is to beprocessed by the substrate processing apparatus 1Q is the same as thatof the substrate which is to be processed by the substrate processingapparatus 1. That is, there can be used the substrate W having a surfacefrom which at least any one of Si, SiN, SiO₂, SiGe, Ge, SiCN, W, TiN,Co, Cu, Ru, and a-C is exposed.

FIG. 24A is a schematic view for describing conditions of the dissolvingliquid supplying step (Step S30). FIG. 24B is a schematic view fordescribing conditions of the rinsing step (Step S31). After the end ofthe processing film forming step (Step S23), the dissolving liquidsupplying step (Step S30) is executed as follows.

First, a heating medium valve 88 is closed. Thereby, the supply of aheating medium to a lower surface of the substrate W is stopped. A gasvalve 53 is also closed. Thereby, the supply of a gas to a space betweena facing surface 6 a of a facing member 6 and the upper surface of thesubstrate W is stopped.

Then, a facing member raising/lowering unit 61 moves a facing member 6to a retract position. In a state that the facing member 6 is positionedat an upper position, the fourth nozzle moving unit 38 moves the fourthmoving nozzle 14 to a processing position. The processing position ofthe fourth moving nozzle 14 is, for example, a central position.

Then, in a state that the fourth moving nozzle 14 is positioned at theprocessing position, a dissolving liquid valve 57 is opened. Thereby, asshown in FIG. 24A, a dissolving liquid is supplied (discharged) from thefourth moving nozzle 14 toward the central region of the upper surfaceof the substrate W in the rotating state (dissolving liquid supplyingstep, dissolving liquid discharging step). The dissolving liquidsupplied to the upper surface of the substrate W spreads over the entireupper surface of the substrate W by a centrifugal force. Thereby, aprocessing film 100 on the upper surface of the substrate W is partiallydissolved in the dissolving liquid and a component dissolved by thedissolving liquid is expelled outside the substrate W together with thedissolving liquid.

The supply of the dissolving liquid to the upper surface of thesubstrate W is continued for a predetermined time of, for example, 60seconds. In the dissolving liquid supplying step, the substrate W isrotated in a predetermined dissolving rotational speed of, for example,800 rpm.

After the dissolving liquid supplying step (Step S30), the rinsing step(Step S31) which will be described hereinafter is executed. In therinsing step, the dissolving liquid is washed away from the substrate Wby a rinse liquid. Since the dissolving liquid is expelled outside thesubstrate W by the rinse liquid, the rinsing step (Step S31) is alsoreferred to as a dissolving liquid expelling step.

In the rinsing step (Step S31), first, the dissolving liquid valve 57 isclosed. Thereby, the supply of the dissolving liquid to the uppersurface of the substrate W is stopped. Then, the fourth nozzle movingunit 38 moves the fourth moving nozzle 14 to the home position. Then, asshown in FIG. 24B, the facing member raising/lowering unit 61 moves thefacing member 6 to the processing position.

Then, in a state that the facing member 6 is positioned at theprocessing position, an upper rinse liquid valve 51 is opened. Thereby,as shown in FIG. 24B, the rinse liquid is supplied (discharged) from thecentral nozzle 12 toward the central region of the upper surface of thesubstrate W in the rotating state (upper rinse liquid supplying step,upper rinse liquid discharging step). The rinse liquid supplied to theupper surface of the substrate W spreads over the entire upper surfaceof the substrate W by a centrifugal force. Thereby, the dissolvingliquid adhering to the upper surface of the substrate W is expelledoutside the substrate W together with the rinse liquid and replaced withthe rinse liquid (dissolving liquid expelling step).

Further, at the same time when the upper rinse liquid valve 51 isopened, the lower rinse liquid valve 86 is opened. Thereby, as shown inFIG. 24B, the rinse liquid is supplied (discharged) from the lowersurface nozzle 13 toward the central region of the lower surface of thesubstrate W in the rotating state (lower rinse liquid supplying step,lower rinse liquid discharging step). Thereby, the dissolving liquidadhering to the upper surface of the substrate W may move from the uppersurface of the substrate W to the lower surface of the substrate W via aperipheral edge portion of the substrate W. Thus, even where thedissolving liquid adheres to the lower surface of the substrate W, thedissolving liquid on the lower surface of the substrate W is washed awayby the rinse liquid.

The supply of the rinse liquid to the upper surface and the lowersurface of the substrate W is continued for a predetermined time of, forexample, 30 seconds. In the rinsing step (Step S31), the substrate W isrotated at a predetermined dissolving liquid expelling rotational speedof, for example, 800 rpm.

As shown in FIG. 23 , after the rinsing step (Step S31), the peelingliquid supplying step (refer to Step S24, and also FIG. 19D) isexecuted. After that, the rinsing step (Step S25)˜the substratecarry-out step (Step S28) are executed sequentially.

Conditions of Peeling Processing Film in Third Preferred Embodiment

Next, conditions in which the processing film 100 is peeled from thesubstrate W in the substrate processing according to the third preferredembodiment will be described in detail with reference to FIG. 25A˜FIG.25D. FIG. 25A˜FIG. 25D are each a schematic view for describingconditions in which the processing film 100 is peeled from the substrateW in the substrate processing according to the third preferredembodiment.

As shown in FIG. 25A, the processing film 100 has the same configurationas the substrate processing according to the second preferredembodiment. That is, as shown in FIG. 25A, the processing film 100 holdsa removal object 103 adhering to a surface layer 150 of the substrate Wand has a high solubility solid 110 and a low solubility solid 111.

In the substrate processing according to the third preferred embodiment,with reference to FIG. 25B, a dissolving liquid is supplied toward anupper surface of the substrate W in a state of formation of theprocessing film 100 (dissolving liquid supplying step). The highsolubility solid 110 is dissolved by the dissolving liquid supplied tothe upper surface of the substrate W. That is, the processing film 100is partially dissolved (dissolving step, partially dissolving step).

By dissolving the high solubility solid 110, the penetrating hole 102 isformed at a portion of the processing film 100 in which the highsolubility solids 110 are unevenly distributed (penetrating hole formingstep). Although the penetrating hole 102 is formed by the dissolvingliquid, the processing film 100 is not yet thereby peeled.

Here, where the solvent remains appropriately in the processing film100, the dissolving liquid partially dissolves the processing film 100,while being dissolved in the solvent remaining on the processing film100. In detail, the dissolving liquid dissolves the high solubilitysolid 110 in the processing film 100 to form the penetrating hole 102,while being dissolved in the solvent remaining in the high solubilitysolid 110. Therefore, the dissolving liquid easily enters the processingfilm 100 (dissolving liquid entry step).

Then, after removal of the dissolving liquid by the rinse liquid, asecond peeling liquid is supplied toward the upper surface of thesubstrate W (peeling liquid supplying step). As shown in FIG. 25C, thesecond peeling liquid passes through the penetrating hole 102 formed bythe dissolving liquid and reaches the upper surface of the substrate W.Thereby, a portion of the upper surface of the substrate W which isexposed by formation of the penetrating hole 102 is hydrophilized(hydrophilization step). Due to hydrophilization of the upper surface ofthe substrate W, the contact angle of pure water for the upper surfaceof the substrate W becomes smaller than 41.7° (contact angle reducingstep).

The second peeling liquid which has reached the upper surface of thesubstrate W acts on an interface between the processing film 100 and thesubstrate W to peel the processing film 100 and remove the peeledprocessing film 100 from the upper surface of the substrate W (peelingremoval step).

In detail, the low solubility component is low in solubility in thesecond peeling liquid and the low solubility solid 111 is hardlydissolved by the second peeling liquid. Therefore, the low solubilitysolid 111 is slightly dissolved only near the surface thereof by thesecond peeling liquid. Accordingly, the second peeling liquid which hasreached near the upper surface of the substrate W via the penetratinghole 102 slightly dissolves a portion of the low solubility solid 111near the upper surface of the substrate W. Thereby, as shown in anenlarged view of FIG. 25C, the second peeling liquid enters a gap G1between the processing film 100 and the upper surface of the substrateW, while gradually dissolving the low solubility solid 111 near theupper surface of the substrate W (peeling liquid entry step).

In the process of the peeling liquid entering the gap G1, with aperipheral edge of the penetrating hole 102 as a starting point, theprocessing film 100 is split into film fragments 105, and as shown inFIG. 25D, and the film fragments 105 of the processing film 100 arepeeled from the substrate W in a state of holding a removal object 103(processing film splitting step, processing film peeling step).

By continuing the supply of the second peeling liquid even after thestart of peeling of the processing film 100, the processing film 100which has become the film fragments 105 is washed away by the secondpeeling liquid in a state of holding the removal object 103. In otherwords, the film fragments 105 which hold the removal object 103 arepushed outside the substrate W and removed from the upper surface of thesubstrate W (processing film removal step, removal object removal step).Thereby, it is possible to satisfactorily clean the upper surface of thesubstrate W.

As described above, according to the third preferred embodiment, thedissolving liquid and the second peeling liquid are each supplied towardthe upper surface of the substrate W in which the processing film 100 isformed. By the supply of the dissolving liquid, the penetrating hole 102is formed in the processing film 100. Then, by the supply of the secondpeeling liquid, the upper surface of the substrate W is hydrophilizedand the processing film 100 is peeled from the upper surface of thesubstrate W. In other words, the formation of the penetrating hole 102,hydrophilization of the substrate W and peeling of the processing film100 are realized by the supply of a different liquid.

Summary of Third Preferred Embodiment

According to the third preferred embodiment, the same effects as thoseof the second preferred embodiment can be obtained. However, in thethird preferred embodiment, unlike the second embodiment, after theformation of the processing film 100 and before the supply of the secondpeeling liquid to the substrate W, the dissolving liquid is supplied tothe substrate W.

In the third preferred embodiment, if a liquid (for example, an alkalineliquid such as ammonia water) larger in difference of solubility betweenthe high solubility solid 110 and the low solubility solid 111 than thesecond peeling liquid is used as the dissolving liquid, it is possibleto peel the low solubility solid 111 from the substrate W by the secondpeeling liquid after formation of the penetrating hole 102 by moreselectively dissolving the high solubility solid 110. In other words, itis possible to suppress the loss of the low solubility solid 111 by thedissolving liquid and suppress the detachment of a removal object fromthe low solubility solid 111. Therefore, it is possible to effectivelypeel the processing film 100 in a state of holding a removal object 103.

Further, the second peeling liquid can be selected, with noconsideration given to the solubility of the high solubility solid 110in the second peeling liquid and, therefore, the degree of freedom isenhanced in selecting the second peeling liquid.

Configuration of Substrate Processing Apparatus According to FourthPreferred Embodiment

FIG. 26 is a schematic partial sectional view which shows a generalconfiguration of a processing unit 2 provided in a substrate processingapparatus 1R according to the fourth preferred embodiment of the presentinvention.

In FIG. 26 , the same configuration as that shown in FIG. 1 ˜FIG. 25Dwhich has been described previously will be given the same referencenumeral as that of FIG. 1 , etc., with a description thereof omitted. InFIG. 26 ˜FIG. 32C which will be described later as well, the samereference numeral as that of FIG. 1 , etc., will be given, with adescription thereof omitted.

The substrate processing apparatus 1R according to the fourth preferredembodiment is different from the substrate processing apparatus 1Qaccording to the third preferred embodiment (refer to FIG. 22 ) mainlyin that the processing unit 2 is provided with a first moving nozzle 9and a hydrophilizing liquid discharged from the first moving nozzle 9 isa second hydrophilizing liquid such as SC1 (ammonia-hydrogen peroxidemixture).

The second hydrophilizing liquid is a liquid capable of appropriatelyhydrophilizing (enhancing the hydrophilicity of) a surface of asubstrate W. The second hydrophilizing liquid is a liquid which containsa substance different from a dissolving liquid or a peeling liquid. Thesecond hydrophilizing liquid is, for example, an oxidizing liquid suchas SC1. The oxidizing liquid is a liquid which contains a substance(oxidizing agent) having an oxidation power. As the oxidizing liquid, inaddition to SC1, there are cited hydrochloric hydrogen peroxide mixedwater solution (HPM), hydrogen peroxide solution, and ozonized water.HPM is also referred to as SC2 (Standard Clean 2).

SC1, SC2 and a hydrogen peroxide solution contain hydrogen peroxide(H₂O₂) as an oxidizing agent. Ozonized water contains ozone (O₃) as anoxidizing agent.

As with the substrate processing shown in FIG. 31 which will bedescribed later, in a case in which the second hydrophilizing liquid issupplied toward a substrate W in which no processing film is formed inan upper surface thereof, a liquid high in solubility in the processingfilm can be used as the second hydrophilizing liquid. Hydrofluoric acid(HF), diluted hydrofluoric acid (DHF), a sulfuric acid/hydrogen peroxidemixture (SPM) and an organic solvent, etc., are cited as theabove-described liquid.

Hydrofluoric acid and diluted hydrofluoric acid contain hydrogenfluoride as an oxidizing agent. SPM contains persulfate as an oxidizingagent. As an organic solvent which can be used as the hydrophilizingliquid in the substrate W in which no processing film is formed on theupper surface, there are cited IPA, etc.

FIG. 27 is a schematic view for describing conditions in which thesurface of the substrate W is hydrophilized by the second hydrophilizingliquid.

Where the oxidizing liquid such as SC1 is used as the secondhydrophilizing liquid, as shown in FIG. 27 , the surface of thesubstrate W is oxidized to form an oxide film 171 on the surface of thesubstrate W. By oxidizing the surface of the substrate W, oxygen atomsbond to a substance exposed from the surface of the substrate W. Oxygenatoms bond to the substance exposed from the surface of the substrate Wand, thereby, the surface of the substrate W is improved inhydrophilicity.

Where the oxidizing liquid is used as the second hydrophilizing liquid,the substrate W can be hydrophilized, regardless of the presence of anorganic substance 170.

The substrate W having a surface from which at least any one of Si, SiN,SiO₂, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru and a-C is exposed can behydrophilized by the second hydrophilizing liquid. In particular, thesubstrate W having a surface from which at least any one of Si, SiN,SiO₂, W, TiN, Co, Cu, Ru and a-C is exposed is easily hydrophilized bythe second hydrophilizing liquid, and the substrate W having a surfacefrom which at least any one of Si, SiN, SiO₂, W, TiN, Co and Cu isexposed is more easily hydrophilized by the second hydrophilizingliquid.

Substrate Processing According to Fourth Preferred Embodiment

FIG. 28 is a flowchart for describing an example of substrate processingby the substrate processing apparatus 1R according to the fourthpreferred embodiment. The substrate processing by the substrateprocessing apparatus 1R is different from the substrate processing(refer to FIG. 23 ) by the substrate processing apparatus 1Q accordingto the third preferred embodiment mainly in that a hydrophilizing liquidsupplying step (Step S40) and a rinsing step (Step S41) are executed inthis order between the rinsing step (Step S31) and the peeling liquidsupplying step (Step S24). Hereinafter, the substrate processing by thesubstrate processing apparatus 1Q will be described, with an emphasisplaced on the hydrophilizing liquid supplying step (Step S40) and therinsing step (Step S41).

It is noted that the substrate W which is to be processed by thesubstrate processing apparatus 1R has the same configuration as thesubstrate which is to be processed by the substrate processing apparatus1P. That is, there can be used the substrate W having a surface fromwhich at least any one of Si, SiN, SiO₂, SiGe, Ge, SiCN, W, TiN, Co, Cu,Ru and a-C is exposed.

FIG. 29A is a schematic view for describing conditions of thehydrophilizing liquid supplying step (Step S40). FIG. 29B is a schematicview for describing conditions of the rinsing step (Step S41).

After the end of the rinsing step (Step S31), the hydrophilizing liquidsupplying step (Step S40) is executed as will be described hereinafter.

First, an upper rinse liquid valve 51 and a lower rinse liquid valve 86are closed. Thereby, the supply of a rinse liquid to the upper surfaceand the lower surface of the substrate W is stopped. A facing memberraising/lowering unit 61 moves a facing member 6 to a retract position.In a state that the facing member 6 is positioned at the retractposition, a first nozzle moving unit 35 moves a first moving nozzle 9 toa processing position. The processing position of the first movingnozzle 9 is, for example, a central position.

Then, in a state the first moving nozzle 9 is positioned at theprocessing position, a hydrophilizing liquid valve 50 is opened.Thereby, as shown in FIG. 29A, a second hydrophilizing liquid issupplied (discharged) from the first moving nozzle 9 toward a centralregion of the upper surface of the substrate W in the rotating state(hydrophilizing liquid supplying step, hydrophilizing liquid dischargingstep). The second hydrophilizing liquid supplied to the upper surface ofthe substrate W spreads over the entire upper surface of the substrate Wby a centrifugal force. Thereby, the entire upper surface of thesubstrate W is hydrophilized by the second hydrophilizing liquid. Thesecond hydrophilizing liquid is expelled outside the substrate W by acentrifugal force.

The supply of the second hydrophilizing liquid to the upper surface ofthe substrate W is continued for a predetermined time of, for example,60 seconds. In the hydrophilizing liquid supplying step, the substrate Wis rotated at a predetermined hydrophilization rotational speed of, forexample, 800 rpm.

After the hydrophilizing liquid supplying step (Step S40), the rinsingstep (Step S41) is executed as will be described hereinafter. In therinsing step, the second hydrophilizing liquid is washed away from thesubstrate W by a rinse liquid. Since the second hydrophilizing liquid isexpelled outside the substrate W by the rinse liquid, the rinsing step(Step S41) is also referred to as a hydrophilizing liquid expellingstep.

In the rinsing step (Step S41), first, the hydrophilizing liquid valve50 is closed. Thereby, the supply of the second hydrophilizing liquid tothe upper surface of the substrate W is stopped.

Then, the first nozzle moving unit 35 moves the first moving nozzle 9 tothe home position. Then, as shown in FIG. 29B, the facing memberraising/lowering unit 61 moves the facing member 6 to the processingposition.

Then, in a state that the facing member 6 is positioned at theprocessing position, the upper rinse liquid valve 51 is opened. Thereby,as shown in FIG. 29B, the rinse liquid is supplied (discharged) from thecentral nozzle 12 toward the central region of the upper surface of thesubstrate W in the rotating state (upper rinse liquid supplying step,upper rinse liquid discharging step). The rinse liquid supplied to theupper surface of the substrate W spreads over the entire upper surfaceof the substrate W by a centrifugal force. Thereby, the secondhydrophilizing liquid adhering to the upper surface of the substrate Wis expelled outside the substrate W together with the rinse liquid andreplaced with the rinse liquid (hydrophilizing liquid expelling step).

Further, at the same time when the upper rinse liquid valve 51 isopened, the lower rinse liquid valve 86 is opened. Thereby, as shown inFIG. 29B, the rinse liquid is supplied (discharged) from the lowersurface nozzle 13 toward the central region of the lower surface of thesubstrate W in the rotating state (lower rinse liquid supplying step,lower rinse liquid discharging step). Thereby, the second hydrophilizingliquid adhering to the upper surface of the substrate W moves from theupper surface of the substrate W to the lower surface of the substrate Wvia a peripheral edge portion of the substrate W. Thus, even where thehydrophilizing liquid adheres to the lower surface of the substrate W,the second hydrophilizing liquid on the lower surface of the substrate Wis washed away by the rinse liquid.

The supply of the rinse liquid to the upper surface and the lowersurface of the substrate W is continued for a predetermined time of, forexample, 30 seconds. In the rinsing step (Step S41), the substrate W isrotated at a predetermined hydrophilizing liquid expelling rotationalspeed of, for example, 800 rpm.

As shown in FIG. 28 , after the rinsing step (Step S41), the peelingliquid supplying step (Step S24)˜the substrate carry-out step (Step S28)are executed sequentially.

Conditions of Peeling of Processing Film in Fourth Preferred Embodiment

Next, conditions in which the processing film 100 is peeled from thesubstrate W in the substrate processing according to the fourthpreferred embodiment will be described in detail with reference to FIG.30A˜FIG. 30E. FIG. 30A˜FIG. 30E are each a schematic view for describingconditions in which the processing film 100 is peeled from the substrateW in the substrate processing according to the fourth preferredembodiment.

As shown in FIG. 30A, the processing film 100 has the same configurationas the substrate processing according to the second preferredembodiment. That is, as shown in FIG. 30A, the processing film 100 holdsa removal object 103 adhering to the surface layer 150 of the substrateW and has a high solubility solid 110 and a low solubility solid 111.

In the substrate processing according to the fourth preferredembodiment, as with the substrate processing according to the thirdpreferred embodiment, with reference to FIG. 30B, a dissolving liquid issupplied toward the upper surface of the substrate W in a state offorming the processing film 100 (dissolving liquid supplying step). Thehigh solubility solid 110 is dissolved by the dissolving liquid suppliedto the upper surface of the substrate W. That is, the processing film100 is partially dissolved (dissolving step, partially dissolving step).

By dissolving the high solubility solid 110, a penetrating hole 102 isformed at a portion of the processing film 100 in which the highsolubility solids 110 are unevenly distributed (penetrating hole formingstep). Although the penetrating hole 102 is formed by the dissolvingliquid, the processing film 100 is not yet thereby peeled.

Here, where the solvent remains appropriately in the processing film100, the dissolving liquid partially dissolves the processing film 100while being dissolving in the solvent remaining on the processing film100. In detail, the dissolving liquid dissolves the high solubilitysolid 110 in the processing film 100 while being dissolved in thesolvent remaining in the high solubility solid 110, thereby forming thepenetrating hole 102. Therefore, the dissolving liquid easily enters theprocessing film 100 (dissolving liquid entry step).

Then, after removal of the dissolving liquid by the rinse liquid, thesecond hydrophilizing liquid is supplied toward the upper surface of thesubstrate W (hydrophilizing liquid supplying step). As shown in FIG.30C, the second hydrophilizing liquid passes through the penetratinghole 102 formed by the dissolving liquid and reaches the upper surfaceof the substrate W. Thereby, a portion of the upper surface of thesubstrate W exposed by formation of the penetrating hole 102 ishydrophilized (hydrophilization step). Due to hydrophilization of theupper surface of the substrate W, a contact angle of pure water for theupper surface of the substrate W becomes smaller than 41.7° (contactangle reducing step). Although the surface of the substrate W ishydrophilized by the second hydrophilizing liquid, the processing film100 is not peeled.

Then, after removal of the second hydrophilizing liquid by the rinseliquid, a second peeling liquid is supplied toward the upper surface ofthe substrate W (peeling liquid supplying step). As shown in FIG. 30D,the second peeling liquid passes through the penetrating hole 102 andreaches the upper surface of the substrate W. The second peeling liquidwhich has reached the upper surface of the substrate W acts on aninterface between the processing film 100 and the substrate W, therebypeeling the processing film 100 and removing the peeled processing film100 from the upper surface of the substrate W (peeling removal step).

A site of the upper surface of the substrate W which is exposed byformation of the penetrating hole 102 is hydrophilized by the secondhydrophilizing liquid and, therefore, the second peeling liquideffectively acts on an interface between a portion of the processingfilm 100 which surrounds the penetrating hole 102 and the substrate W.In other words, as shown in an enlarged view of FIG. 30D, the secondpeeling liquid acts quickly to enter a gap G1 between the processingfilm 100 and the substrate W (peeling liquid entry step).

In detail, the low solubility component is low in solubility in thesecond peeling liquid and the low solubility solid 111 is hardlydissolved by the peeling liquid. Therefore, the low solubility solid 111is slightly dissolved only near the surface thereof by the secondpeeling liquid. Therefore, the second peeling liquid which has reachednear the upper surface of the substrate W via the penetrating hole 102slightly dissolves a portion of the low solubility solid 111 near theupper surface of the substrate W. Thereby, as shown in an enlarged viewof FIG. 30D, the second peeling liquid enters the gap G1 between theprocessing film 100 and the upper surface of the substrate W whilegradually dissolving the low solubility solid 111 near the upper surfaceof the substrate W (peeling liquid entry step).

In the process of the second peeling liquid entering the gap G1, with aperipheral edge of the penetrating hole 102 as a starting point, theprocessing film 100 is split into film fragments 105. As shown in FIG.30E, the film fragments 105 of the processing film 100 are peeled fromthe substrate W in a state of holding the removal object 103 (processingfilm splitting step, processing film peeling step).

By continuing the supply of the second peeling liquid, the processingfilm 100 which has become the film fragments 105 is washed away by thesecond peeling liquid in a state of holding the removal object 103. Inother words, the film fragments 105 which hold the removal object 103are pushed outside the substrate W and removed from the upper surface ofthe substrate W (processing film removal step, removal object removalstep). Thereby, it is possible to satisfactorily clean the upper surfaceof the substrate W.

As described above, according to the fourth preferred embodiment, thedissolving liquid, the second hydrophilizing liquid and the secondpeeling liquid are each supplied toward the upper surface of thesubstrate W in which the processing film 100 is formed. By the supply ofthe dissolving liquid, the penetrating hole 102 is formed in theprocessing film 100. By the supply of the second hydrophilizing liquid,the upper surface of the substrate W is hydrophilized. Then, by thesupply of the second peeling liquid, the processing film 100 is peeledfrom the upper surface of the substrate W. In other words, the formationof the penetrating hole 102, hydrophilization of the substrate W andpeeling of the processing film 100 are realized by the supply of adifferent liquid.

Summary of Fourth Preferred Embodiment

According to the fourth preferred embodiment, the same effects as thoseof the third preferred embodiment can be obtained. However, in thefourth preferred embodiment unlike the third preferred embodiment, afterthe supply of the dissolving liquid to the substrate W and before thesupply of the second peeling liquid to the substrate W, the secondhydrophilizing liquid is supplied to the substrate W.

In the fourth preferred embodiment, the upper surface of the substrate Wcan be sufficiently hydrophilized by the second hydrophilizing liquid.Therefore, the second peeling liquid can be selected, with thehydrophilization capacity of the second peeling liquid not taken intoaccount.

Specifically, if a mass percent concentration of IPA in the secondpeeling liquid is not less than 12%, it is possible to sufficientlyenhance the hydrophilicity of the upper surface of the substrate W. Ifthe mass percent concentration of IPA in the second peeling liquid isnot less than 1% and not more than 33%, it is possible to peel theprocessing film 100 from the substrate W, while appropriately dissolvingthe processing film 100 on the substrate W. Therefore, even if thesecond peeling liquid with the mass percent concentration of IPA beingnot less than 1% and less than 12% is used, it is possible tosufficiently peel the processing film 100. Therefore, the use of thesecond hydrophilizing liquid makes it possible to select the secondpeeling liquid, with a degree of hydrophilization by the second peelingliquid (hydrophilizing power of the second peeling liquid) not takeninto account. Therefore, the degree of freedom is enhanced in selectingthe second peeling liquid.

Since there can be selected the second peeling liquid suitable forpeeling the processing film 100, with the hydrophilizing power of thesecond peeling liquid not taken into account, it is possible toeffectively peel the processing film 100 in a state of holding theremoval object 103.

Another Example of Substrate Processing in Fourth Preferred Embodiment

Use of the substrate processing apparatus 1R in the fourth preferredembodiment makes it also possible to execute the substrate processingshown in FIG. 31 . The substrate processing shown in FIG. 31 isdifferent from the substrate processing shown in FIG. 28 in that thehydrophilizing liquid supplying step (Step S40) and the rinsing step(Step S41) are not executed but a prior hydrophilization step (StepS50), a rinsing step (Step S51) and a replacing step (Step S52) areexecuted before the processing liquid supplying step (Step S22).

FIG. 32A˜FIG. 32C are each a schematic view for describing conditions ofthe substrate processing shown in FIG. 31 .

First, after the substrate carry-in step (Step S21), the priorhydrophilization step (Step S50) is executed. Specifically, as shown inFIG. 32A, a second hydrophilizing liquid is supplied (discharged) fromthe first moving nozzle 9 toward the upper surface of the substrate W,that is, toward a central region of the upper surface of the substrate Win the rotating state (prior hydrophilizing liquid supplying step, priorhydrophilizing liquid discharging step). The second hydrophilizingliquid supplied to the upper surface of the substrate W spreads over theentire upper surface of the substrate W by a centrifugal force. Thereby,the entire upper surface of the substrate W is hydrophilized by thesecond hydrophilizing liquid. The second hydrophilizing liquid isexpelled outside the substrate W by a centrifugal force.

In the prior hydrophilization step (Step S50), the second hydrophilizingliquid is supplied toward the substrate W in which no processing film isformed on the upper surface thereof. Therefore, as described previously,it is possible to use, as the second hydrophilizing liquid, a liquidwhich is high in solubility in a processing film. Therefore, as thesecond hydrophilizing liquid, there can be used an oxidizing liquid suchas SC1, SC2, hydrogen peroxide solution, ionized water, SPM,hydrofluoric acid, etc., and an organic solvent such as IPA, etc.

With reference to FIG. 32B, the rinsing step (Step S51) similar to therinsing step (Step S41) is executed after the prior hydrophilizationstep (Step S50). In the rinsing step (Step S51), the hydrophilizingliquid is washed away from the substrate W by the rinse liquid. Sincethe hydrophilizing liquid is expelled outside the substrate W by therinse liquid, the rinsing step (Step S51) is also referred to as a priorhydrophilizing liquid expelling step.

With reference to FIG. 32C, after the rinsing step (Step S51), thereplacing step (Step S52) in which the rinse liquid on the substrate Wis replaced with the replacing liquid such as an organic solvent isexecuted. In the replacing step, the rinse liquid on the substrate W isreplaced with the residue removing liquid as a replacing liquid.

Specifically, an upper rinse liquid valve 51 and a lower rinse liquidvalve 86 are closed. Thereby, the supply of the rinse liquid to theupper surface and the lower surface of the substrate W is stopped. Afacing member 6 is kept at a processing position.

In a state that the facing member 6 is kept at the processing position,an organic solvent valve 52 is opened. Thereby, as shown in FIG. 32C,the replacing liquid (residue removing liquid) which is an organicsolvent such as IPA is supplied (discharged) from a central nozzle 12toward the central region of the upper surface of the substrate W in therotating state (replacing liquid supplying step, replacing liquiddischarging step). The central nozzle 12 is an example of a replacingliquid supplying unit.

The replacing liquid supplied from the central nozzle 12 to the uppersurface of the substrate W spreads radially by receiving a centrifugalforce and spreads over the entire upper surface of the substrate W.Thereby, the rinse liquid on the substrate W is replaced with thereplacing liquid.

In the replacing step, the discharge of the replacing liquid from thecentral nozzle 12 is continued for a predetermined time of, for example,10 seconds. In the replacing step, the substrate W is rotated at apredetermined replacing rotational speed of, for example, 300 rpm˜1500rpm. The substrate W is not required to be rotated at a fixed rotationalspeed in the replacing step. For example, a spin motor 23 may rotate thesubstrate W at 300 rpm at the start of supplying the replacing liquidand accelerate the rotation of the substrate W until the rotationalspeed of the substrate W reaches 1500 rpm while supplying the replacingliquid to the substrate W.

The replacing liquid such as IPA discharged from the second tube 32 issupplied to the upper surface of the substrate W covered with a liquidfilm of the rinse liquid, and the processing liquid is supplied to theupper surface of the substrate W covered with a liquid film of thereplacing liquid. When the replacing liquid is supplied to the uppersurface of the substrate W covered with the liquid film of the rinseliquid, a large portion of the rinse liquid on the substrate W is pushedaway by the replacing liquid and expelled from the substrate W.

A remaining trace amount of the rinse liquid is dissolved in thereplacing liquid and diffused in the replacing liquid. The diffusedrinse liquid is expelled from the substrate W together with thereplacing liquid. Therefore, it is possible to efficiently replace therinse liquid on the substrate W with the replacing liquid. Due to thesame reason, the replacing liquid on the substrate W can be efficientlyreplaced with the processing liquid. Thereby, it is possible to reducean amount of the rinse liquid contained in the processing liquid on thesubstrate W.

Thereafter, as shown in FIG. 31 , the processing liquid supplying step(Step S22)˜the substrate carry-out step (Step S28) are executedsequentially.

In the substrate processing shown in FIG. 31 , before the supply of theprocessing liquid to the upper surface of the substrate W, that is, theupper surface of the substrate W is hydrophilized in advance. Therefore,the processing film 100 is formed in the hydrophilized upper surface ofthe substrate W. The processing film 100 can be, therefore, peeledeffectively from the substrate W by the second peeling liquid.

<Experiment of Measuring Contact Angle by Using Diluted IPA>

Hereinafter, a description will be given of the results of a contactangle measuring experiment in which a contact angle of diluted IPA forthe surface of the substrate is measured.

In the experiment, an experimental substrate in which Ru was exposedfrom a surface thereof and an experimental substrate in which baresilicon was exposed from the surface were used. The experimentalsubstrate in which Ru is exposed from the surface is a substrate inwhich a Ru film is formed by a CVD method. The experimental substrateused in the experiment is a small substrate in a square shape with thelength of a side of 3 cm in plan view, as with the previously-describedexperiment.

The experimental substrate in which Ru is exposed from the surface isprocessed in advance with IPA and a contact angle of pure water for theexperimental substrate is 60°. The experimental substrate in which Si isexposed from the surface is processed in advance with hydrofluoric acidwith 0.5% of a mass percent concentration, and a contact angle of purewater for the experimental substrate is 62°.

In the experiment, diluted IPA which was formulated in five differentconcentrations of IPA was dropped onto an experimental substrate tomeasure a contact angle of diluted IPA at each different concentrationof IPA for the surface of the experimental substrate. The contact angleof diluted IPA at each of the five different concentrations of IPA wasmeasured in each of the experimental substrates.

FIG. 33 is a graph which shows a relationship between the concentrationsof IPA in diluted IPA and the contact angle of diluted IPA for thesurface of the experimental substrate. The horizontal axis of FIG. 33indicates a concentration (mass percent concentration) of IPA in dilutedIPA. The vertical axis of FIG. 33 indicates a contact angle of dilutedIPA for the surface of the experimental substrate.

As shown in FIG. 33 , even the experimental substrate in which any oneof Ru and Si was exposed from the surface of the experimental substratewas decreased in contact angle according to an increase in concentrationof IPA in diluted IPA. The experiment has yielded such effects that, inthe experimental substrate in which Ru is exposed from the surface, thecontact angle becomes less than 41.7° when the concentration of IPA isnot less than about 12%. Such effects have been also yielded that, inthe experimental substrate in which bare silicon is exposed from thesurface, the contact angle becomes less than 41.7° when theconcentration of IPA is not less than about 15%. Therefore, theexperiment has suggested a possibility that, when the concentration ofIPA is not less than about 12%, the surface of the substrate may besufficiently hydrophilized.

<Experiment of Peeling Processing Film by Using Diluted IPA>

Hereinafter, a description will be given of the results of a processingfilm peeling experiment in which the processing film is peeled off byusing diluted IPA.

In the experiment, a substrate in which Si was exposed from a surfacethereof was used as an experimental substrate. The experimentalsubstrate used in the experiment is also a small substrate in a squareshape with the length of one side of 3 cm in plan view, as with thepreviously-described experiment. The experimental substrate is processedin advance with IPA, and the contact angle of pure water for theexperimental substrate is 23°.

In the experiment, a processing liquid was dropped onto the surface ofthe experimental substrate to form a processing film, diluted IPA wasdropped onto the surface of the experimental substrate on which theprocessing film was formed, and conditions of removing the processingfilm were microscopically observed.

FIG. 34 shows microscopic images for describing conditions of thesurface of the experimental substrate when diluted IPA was dropped ontoan experimental substrate in which a processing film was formed on asurface thereof. As shown in FIG. 34 , when the mass percentconcentrations of IPA in diluted IPA are 1%, 25% and 33%, the processingfilm is peeled off by diluted IPA. In detail, when the mass percentconcentrations of IPA in diluted IPA are 1%, 25% and 33%, diluted IPAenters between the processing film and the experimental substrate todevelop wrinkles 400 on the processing film. On the other hand, when themass percent concentration of IPA in diluted IPA is 50%, the processingfilm is dissolved by diluted IPA. Therefore, the experiment has revealedthat, when the concentration of IPA is not less than 1% and not morethan 33%, the processing film can be peeled from the surface of thesubstrate.

The experiment has also revealed that, when the concentration of IPA isnot less than 50%, the processing film is dissolved so as not to bepeeled. It is thus presumed that the processing film is disposed to beeasily dissolved in an organic solvent such as IPA rather than in water.

<Details of Processing Liquid>

Hereinafter, a description will be given of each component in theprocessing liquid used in the above-described preferred embodiments.

Hereinafter, expressions of “C_(x˜y),” “C_(x)˜C_(y),” and “C_(x),” etc.,indicate the number of carbons in a molecule or a substituent. Forexample, C_(1˜6) alkyl indicates an alkyl chain (methyl, ethyl, propyl,butyl, pentyl, hexyl, etc.) having not less than one and not more thansix carbons.

When a polymer has plural types of repeating units, these repeatingunits are copolymerized. Unless specifically mentioned otherwise, thecopolymerization may be any one of alternating copolymerization, randomcopolymerization, block copolymerization, graft copolymerization or amixture of them. When a polymer and a resin are expressed by astructural formula, n, m, etc., which are written together inparentheses indicate the number of repetitions.

<Low Solubility Component>

The (A) low solubility component contains at least one of novolac,polyhydroxystyrene, polystyrene, a polyacrylic acid derivative, apolymaleic acid derivative, polycarbonate, a polyvinyl alcoholderivative, a polymethacrylic acid derivative and a copolymer of acombination of the above. The (A) low solubility component maypreferably contain at least one of novolac, polyhydroxystyrene, apolyacrylic acid derivative, polycarbonate, a polymethacrylic acidderivative and a copolymer of a combination of the above. Morepreferably, the (A) low solubility component may contain at least one ofnovolac, polyhydroxystyrene, polycarbonate and a copolymer of acombination of the above. Novolac may be phenol novolac.

The processing liquid may contain one or a combination of two or more ofthe above-described preferable examples as the (A) low solubilitycomponent. For example, the (A) low solubility component may containboth novolac and polyhydroxystyrene.

The (A) low solubility component is formed into a film by being dried,and the film is peeled while still holding a removal object withoutbeing largely dissolved in the peeling liquid, which is one preferredmode. Permissible is a mode where a very small portion of the (A) lowsolubility component is dissolved by the peeling liquid.

Preferably, the (A) low solubility component does not contain fluorineand/or silicon and more preferably it contains neither element.

The copolymerization is preferably random copolymerization or blockcopolymerization.

Although not intended to restrict the scope of the claims in the presentinvention, the compounds expressed by the following Chemical Formulae1˜7 can be cited as specific examples of the (A) low solubilitycomponent.

(Asterisk* indicates bonding to an adjacent constituent unit.)

(R signifies a substituent such as a C_(1˜4) alkyl, etc. Asterisk*indicates bonding to an adjacent constituent unit.)

(Me signifies a methyl group. Asterisk* indicates bonding to an adjacentconstituent unit.)

A weight average molecular weight (Mw) of the (A) low solubilitycomponent is preferably 150˜500,000, more preferably 300˜300,000, evenmore preferably 500˜100,000 and yet even more preferably 1,000˜50,000.

The (A) low solubility component can be obtained by synthesis. It canalso be purchased. In the case of purchase, the following can be citedas examples of suppliers. The (A) polymer can also be synthesized by asupplier.

Novolac: Showa Kasei Kogyo Co., Ltd., Asahi Yukizai Corporation, GuneiChemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.

Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co.,Ltd., Toho Chemical Industry Co., Ltd.

Polyacrylic acid derivative: Nippon Shokubai Co., Ltd.

Polycarbonate: Sigma-Aldrich

Polymethacrylic acid derivative: Sigma-Aldrich

In comparison to a total mass of the processing liquid, the (A) lowsolubility component is 0.1˜50 mass % preferably 0.5˜30 mass %, morepreferably 1˜20 mass % and even more preferably 1˜10 mass %. In otherwords, based on the total mass of the processing liquid as 100 mass %which is a reference, the (A) low solubility component is 0.1˜50 mass %.That is, “in comparison to” can be rephrased as “based on.” The sameapplies hereinafter, unless specifically mentioned otherwise.

<High Solubility Component>

The (B) high solubility component is a (B′) crack promoting component.The (B′) crack promoting component contains hydrocarbon, furthercontains a hydroxy group (—OH) and/or a carbonyl group (—C(═O)—). Wherethe (B′) crack promoting component is a polymer, one type of constituentunit contains hydrocarbon in each unit and further has a hydroxy groupand/or a carbonyl group. As the carbonyl group, carboxylic acid (—COOH),aldehyde, ketone, ester, amide and enone, etc., can be cited, andcarboxylic acid is preferable.

Although not intended to restrict the scope of the claims or not boundby theory, when the processing liquid is dried, the processing film isformed on the substrate and the peeling liquid peels the processingfilm, the (B) high solubility component may produce a portion that maygive rise to peeling of the processing film. Therefore, the (B) highsolubility component is preferably higher in solubility in the peelingliquid than the (A) low solubility component. As a mode where the (B′)crack promoting component contains ketone as the carbonyl group, cyclichydrocarbon can be cited. As specific examples, 1,2-cyclohexanedione and1,3-cyclohexanedione can be cited.

As a more specific mode, the (B) high solubility component is expressedby at least one of (B-1), (B-2) and (B-3) given below.

(B-1) contains 1˜6 of Chemical Formula 8 given below as a constituentunit (preferably 1˜4) and each constituent unit is a compound which isbonded by a linking group (linker L₁). Here, the linker L₁ may be asingle bond or C_(1˜6) alkylene. The above C_(1˜6) alkylene bonds aconstituent unit as a linker and is not limited to a divalent group. Itis preferably a divalent to tetravalent group. The C_(1˜6) alkylene maybe straight-chained or branched.

Cy₁ is a hydrocarbon ring with C_(5˜30), preferably phenyl, cyclohexaneor naphthyl and more preferably phenyl. As a preferable mode, the linkerL₁ bonds a plurality of Cy₁.

R₁ is independently C_(1˜5) alkyl and preferably, methyl, ethyl, propyl,or butyl. The above C_(1˜5) alkyl may be straight-chained or branched.

n_(b1) is 1, 2 or 3, preferably 1 or 2 and more preferably 1. n_(b1), is0, 1, 2, 3 or 4 and preferably 0, 1 or 2.

Chemical Formula 9 given below is a chemical formula in which theconstituent unit described in Chemical Formula 8 is expressed by using alinker L₉. The linker L₉ is preferably a single bond, methylene,ethylene or propylene.

Although not intended to restrict the scope of the claims,2,2-bis(4-hydroxyphenyl)propane, 2,2′-methylenebis(4-methylphenol),2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol,1,3-cyclohexanediol, 4,4′-dihydroxybiphenyl, 2,6-naphthalenediol,2,5-di-tert-butylhydroquinone, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethanecan be cited as preferable examples of (B-1). These may be obtained bypolymerization or condensation.

2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol shown inChemical Formula 10 given below is taken as an example and will bedescribed. This compound has three constituent units of Chemical Formula8 in (B-1) and the constituent units are bonded by a linker L₁(methylene). n_(b1)=n_(b1′)=1 and R1 is methyl.

(B-2) is expressed by Chemical Formula 11 given below.

R₂₁, R₂₂, R₂₃ and R₂₄ are independently hydrogen or C_(1˜5) alkyl,preferably hydrogen, methyl, ethyl, t-butyl or isopropyl, morepreferably, hydrogen, methyl or ethyl, and even more preferably, methylor ethyl.

A linker L₂₁ and a linker L₂₂ are independently C_(1˜20) alkylene,C_(1˜20) cycloalkylene, C_(2˜4) alkenylene, C_(2˜4) alkinylene orC_(6˜20) arylene. These groups may be replaced with C_(1˜5) alkyl orhydroxyl. Here, alkenylene means a divalent hydrocarbon with one or moredouble bonds, and alkinylene means a divalent hydrocarbon group with oneor more triple bond. The linker L₂₁ and the linker L₂₂ are preferablyC_(2˜4) alkylene, acetylene (C₂ alkinylene) or phenylene, morepreferably, C_(2˜4) alkylene or acetylene and even more preferablyacetylene.

n_(b2) is 0, 1 or 2, preferably 0 or 1 and more preferably 0.

Although not intended to restrict the scope of the claims, 3,6-dimethyl4-octyne-3,6-diol, 2,5-dimethyl 3-hexyne-2,5-diol can be cited aspreferable examples of (B-2). As another embodiment, 3-hexyne-2,5-diol,1,4-butynediol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol,cis-1,4-dihydroxy-2-butene, 1,4-benzenedimethanol can be cited aspreferable examples of (B-2).

The (B-3) contains the constituent unit expressed by Chemical Formula 12given below and a polymer with a weight average molecular weight (Mw) of500˜10,000. Mw is preferably 600˜5,000 and more preferably 700˜3,000.

Here, R₂₅ is —H, —CH₃ or —COOH and preferably —H or —COOH. One (B-3)polymer may contain two or more constituent units, each of which isexpressed by Chemical Formula 12.

Although not intended to restrict the scope of the claims, polymers ofacrylic acid, maleic acid or combinations of them can be cited aspreferable examples of the (B-3) polymer. Polyacrylic acids and maleicacid/acrylic acid copolymers are more preferable examples.

In the case of copolymerization, random copolymerization or blockcopolymerization is preferable, and random copolymerization is morepreferable.

A description will be given, as an example, by citing a maleicacid/acrylic acid copolymer shown in Chemical Formula 13 below. Thecopolymer is contained in the (B-3) and has two types of constituentunits expressed by Chemical Formula 12. In one constituent unit, R₂₅ is—H, and in another constituent unit, R₂₅ is —COOH.

Obviously, the processing liquid may contain one or a combination of twoor more of the above-described preferable examples as the (B) highsolubility component. For example, the (B) high solubility component maycontain both 2,2-bis(4-hydroxyphenyl) propane and3,6-dimethyl-4-octyne-3,6-diol.

The (B) high solubility component may be 80˜10,000 in molecular weight.The high solubility component is preferably 90˜5000 in molecular weightand more preferably 100˜3000. Where the (B) high solubility component isa resin, a polymeride or a polymer, the molecular weight is expressed bythe weight average molecular weight (Mw).

The (B) high solubility component can be obtained by synthesis orpurchase. As suppliers, Sigma-Aldrich, Tokyo Chemical Industry, Co.,Ltd., and Nippon Shokubai Co., Ltd., can be cited.

In the processing liquid, the (B) high solubility component ispreferably 1˜100 mass % in comparison to the mass of the (A) lowsolubility component and more preferably 1˜50 mass %. In the processingliquid, the (B) high solubility component is even more preferably 1˜30mass % in comparison to the mass of the (A) low solubility component.

<Solvent>

The (C) solvent preferably contains an organic solvent. The (C) solventmay have volatility. Having volatility means that the solvent is higherin volatility in comparison to water. For example, a boiling point atone atmospheric pressure of the (C) solvent is preferably 50˜250° C. Theboiling point at one atmospheric pressure of the solvent is morepreferably 50˜200° C. and even more preferably 60˜170° C. The boilingpoint at one atmospheric pressure of the solvent is yet even morepreferably 70˜150° C. It is permissible for the (C) solvent to contain asmall amount of pure water. The amount of pure water contained in the(C) solvent is preferably not more than 30 mass % in comparison to theentire (C) solvent. The amount of pure water contained in the solvent ismore preferably not more than 20 mass % and even more preferably notmore than 10 mass %. The amount of pure water contained in the solventis yet even more preferably not more than 5 mass % It is also apreferred embodiment that the solvent does not contain pure water (0mass %). The pure water is preferably DIW.

As the organic solvent, an alcohol such as isopropanol (IPA), etc., anethylene glycol monoalkyl ether such as ethylene glycol monomethylether, ethylene glycol monoethyl ether, etc., an ethylene glycolmonoalkyl ether acetate such as ethylene glycol monomethyl etheracetate, ethylene glycol monoethyl ether acetate, etc., a propyleneglycol monoalkyl ether such as propylene glycol monomethyl ether (PGME),propylene glycol monoethyl ether (PGEE), etc., a propylene glycolmonoalkyl ether acetate such as propylene glycol monomethyl etheracetate (PGMEA), propylene glycol monoethyl ether acetate, etc., alactic acid ester such as methyl lactate, ethyl lactate (EL), etc., anaromatic hydrocarbon such as toluene, xylene, etc., a ketone such asmethyl ethyl ketone, 2-heptanone, cyclohexanone, etc., an amide such asN,N-dimethylacetamide, N-methylpyrrolidone, etc., or a lactone such asy-butyrolactone, etc., can be cited. These organic solvents can be usedalone or two or more types can be mixed and used.

As a preferred mode, the organic solvent contained in the (C) solvent isselected from IPA, PGME, PGEE, EL, PGMEA and any combination thereof. Ifthe organic solvent is a combination of two types, a volume ratiothereof is preferably 20:80˜80:20 and more preferably 30:70˜70:30.

In comparison to the entire mass of the processing liquid, the (C)solvent is 0.1˜99.9 mass %. In comparison to the entire mass of theprocessing liquid, the (C) solvent is preferably 50˜99.9 mass % and morepreferably 75˜99.5 mass %. In comparison to the entire mass of theprocessing liquid, the (C) solvent is even more preferably 80˜99 mass %and yet even more preferably 85˜99 mass %.

<Other Additives>

The processing liquid of the present invention may further contain (D)other additives. As a mode of the present invention, the (D) otheradditives may include a surfactant, an acid, a base, an antibacterialagent, a bactericide, an antiseptic, and an antifungal agent(preferably, a surfactant) or may include a combination of any of theabove.

As a mode of the present invention, in comparison to the mass of the (A)low solubility component in the processing liquid, the (D) otheradditives (the sum amount in a plurality of additives) is 0˜100 mass(preferably 0˜10 mass %, more preferably 0˜5 mass % and even morepreferably 0˜3 mass %, and yet even more preferably 0˜1 mass %). Theprocessing liquid (D) which is free of other additives (0 mass %) isalso a mode of the present invention.

<Corrosion Preventive Component>

As (F) corrosion preventive components, in addition to BTA, uric acid,caffeine, butelline, adenine, glyoxylic acid, glucose, fructose, mannoseetc., are cited.

Other Preferred Embodiments

The present invention shall not be limited to the preferred embodimentsdescribed above but may be executed further in yet other embodiments.

The hydrophilization of the upper surface of the substrate W in theabove-described first preferred embodiment may be, for example, carriedout by such methods as UV irradiation, plasma processing, oxygen ashing,etc., that is, by a method other than processing by the firsthydrophilizing liquid.

Further, in the above-described first preferred embodiment, the sameorganic solvent is used as the replacing liquid and the residue removingliquid. However, the organic solvent used as the replacing liquid andthe organic solvent used as the residue removing liquid may be differentfrom each other, if a nozzle for discharging the organic solvent as thereplacing liquid and a nozzle for discharging the residue removingliquid are each provided. For example, methanol can be used as thereplacing liquid, and IPA can be used as the residue removing liquid.

Further, in the above-described first preferred embodiment, theprocessing film 100 is partially dissolved by the peeling liquid, bywhich the penetrating hole 102 is formed and the peeling liquid reachesan interface between the processing film 100 and the substrate W via thepenetrating hole 102. However, it is not always necessary to form amacroscopically visible penetrating hole 102. There may be a possibilitythat the high solubility solid 110 in the processing film 100 isdissolved by the peeling liquid, the peeling liquid reaches an interfacebetween the processing film 100 and the substrate W via a space formedin the processing film 100.

In the above-described first preferred embodiment, the nozzle fordischarging each processing fluid is not limited to that describedabove. For example, in the above-described preferred embodiments, theprocessing liquid, the hydrophilizing liquid and the peeling liquid aredischarged from the moving nozzle toward the upper surface of thesubstrate W, and the rinse liquid, the organic solvent and the gas aredischarged from the fixed nozzle (central nozzle 12) toward the uppersurface of the substrate W. However, the rinse liquid, the organicsolvent and the gas may be configured so as to be discharged from themoving nozzle. In addition to the rinse liquid, the organic solvent andthe gas, the processing liquid, the hydrophilizing liquid and thepeeling liquid may also be discharged from the central nozzle 12.

Further, in the fourth preferred embodiment, the upper surface of thesubstrate W may be hydrophilized in the prior hydrophilization step(Step S51) by a method such as UV irradiation, plasma processing andoxygen ashing, etc., other than processing by the second hydrophilizingliquid.

Further, in the substrate processing shown in FIG. 31 , the same organicsolvent is used as the replacing liquid and the residue removing liquid.However, the organic solvent used as the replacing liquid and theorganic solvent used as the residue removing liquid may be differentfrom each other, if a nozzle for discharging the organic solvent as thereplacing liquid and a nozzle for discharging the residue removingliquid are each provided. For example, methanol can be used as thereplacing liquid and IPA can be used as the residue removing liquid.

The nozzle for discharging each of the processing fluids (processingliquid, peeling liquid, rinse liquid, residue removing liquid,dissolving liquid, hydrophilizing liquid, heating medium, inert gas andreplacing liquid) is not required to assume the modes shown in theabove-described second to fourth preferred embodiments. For example, inthe fourth preferred embodiment, such an configuration may also bepossible that no first moving nozzle 9 is provided and the fourth movingnozzle 14 discharges the second hydrophilizing liquid and the dissolvingliquid.

For example, where the second hydrophilizing liquid is SC1 and thedissolving liquid is ammonia water, a hydrogen peroxide solution can bemixed with the dissolving liquid to formulate the second hydrophilizingliquid. Therefore, only ammonia water is supplied to the fourth movingnozzle 14 and, thereby, the dissolving liquid can be discharged from thefourth moving nozzle 14. Ammonia water and a hydrogen peroxide solutionare supplied to the fourth moving nozzle 14 and, thereby, SC1 can bedischarged from the fourth moving nozzle 14.

An configuration that all the processing fluids are discharged from themoving nozzle or an configuration that all the processing fluids aredischarged from the fixed nozzle disposed outside the substrate W inplan view makes it unnecessary to provide the facing member 6.

Further, in the above-described second to fourth preferred embodiments,the macroscopically visible penetrating hole 102 is not necessarilyformed on the processing film 100. A space may be formed on theprocessing film 100 by dissolution of the high solubility solid 110, andthe hydrophilizing liquid and the peeling liquid may pass through thespace and reach an interface between the substrate W and the processingfilm 100.

The modified example of the second preferred embodiment shown in FIG. 21is applicable to the substrate processing apparatus 1Q according to thethird preferred embodiment and to the substrate processing apparatus 1Raccording to the fourth preferred embodiment. In other words, also inthe peeling liquid supplying step (Step S24) of the substrate processingaccording to the third preferred embodiment and the peeling liquidsupplying step (Step S24) of the substrate processing according to thefourth preferred embodiment, during the supply of the second peelingliquid to the upper surface of the substrate W, the opening degree ofthe organic solvent adjusting valve 93B and that of the pure wateradjusting valve 94B can be adjusted to adjust the concentration of anorganic solvent in the second peeling liquid which is supplied to theupper surface of the substrate W (organic solvent concentrationadjusting step).

Further, in the substrate processing shown in FIG. 28 and FIG. 31 , thedissolving liquid supplying step (Step S30) and the rinsing step (StepS31) can be omitted.

Further, in the substrate processing shown in FIG. 18 , FIG. 23 and FIG.28 , the prior hydrophilization step (Step S50), the rinsing step (StepS51) and the replacing step (Step S52) can be executed.

In detail, in the substrate processing shown in FIG. 18 , after thesubstrate carry-in step (Step S21), the prior hydrophilization step(Step S50), the rinsing step (Step S51) and the replacing step (StepS52) may be executed, and thereafter, the processing liquid supplyingstep (Step S22), the processing film forming step (Step S23), thepeeling liquid supplying step (Step S24), the rinsing step (Step S25),the residue removing liquid supplying step (Step S26), the spin dryingstep (Step S27) and the substrate carry-out step (Step S28) may beexecuted in this order.

Similarly, in the substrate processing shown in FIG. 23 , after thesubstrate carry-in step (Step S21), the prior hydrophilization step(Step S50), the rinsing step (Step S51) and the replacing step (StepS52) may be executed, and, thereafter, the processing liquid supplyingstep (Step S22), the processing film forming step (Step S23), thedissolving liquid supplying step (Step S30), the rinsing step (StepS31), the peeling liquid supplying step (Step S24), the rinsing step(Step S25), the residue removing liquid supplying step (Step S26), thespin drying step (Step S27) and the substrate carry-out step (Step S28)may be executed in this order.

Similarly, in the substrate processing shown in FIG. 28 , after thesubstrate carry-in step (Step S21), the prior hydrophilization step(Step S50), the rinsing step (Step S51) and the replacing step (StepS52) may be executed and, thereafter, the processing liquid supplyingstep (Step S22), the processing film forming step (Step S23), thedissolving liquid supplying step (Step S30), the rinsing step (StepS31), the hydrophilizing liquid supplying step (Step S40), the rinsingstep (Step S41), the peeling liquid supplying step (Step S24), therinsing step (Step S25), the residue removing liquid supplying step(Step S26), the spin drying step (Step S27) and the substrate carry-outstep (Step S28) may be executed in this order.

Further, in the substrate processing shown in FIG. 28 , the rinsing step(Step S31) can be omitted where the hydrophilizing liquid hascompatibility with the dissolving liquid, and the rinsing step (StepS41) can be omitted where the hydrophilizing liquid has compatibilitywith the peeling liquid. In the substrate processing shown in FIG. 23and FIG. 31 , the rinsing step (Step S31) can be omitted where thedissolving liquid has compatibility with the peeling liquid.

In the present specification, when a numeral range is indicated by using“˜” or “−,” unless specifically mentioned otherwise, the range includesboth endpoints and the units are the same.

While preferred embodiments of the present invention have been describedabove, it is to be understood that variations and modifications will beapparent to those skilled in the art without departing from the scopeand spirit of the present invention. The scope of the present invention,therefore, is to be determined solely by the following claims.

What is claimed is:
 1. A substrate processing method comprising: ahydrophilization step of hydrophilizing a surface of a substrate; aprocessing liquid supplying step of supplying a processing liquid to thehydrophilized surface of the substrate; a processing film forming stepin which the processing liquid supplied to the surface of the substrateis solidified or cured to form, on the surface of the substrate, aprocessing film which holds a removal object present on the surface ofthe substrate; and a peeling step in which a peeling liquid is suppliedto the surface of the substrate, thereby peeling the processing film ina state of holding the removal object from the surface of the substrate,wherein the peeling step includes a penetrating hole forming step offorming a penetrating hole in the processing film by partiallydissolving the processing film by the peeling liquid, wherein thehydrophilization step includes a contact angle reducing step in whichthe contact angle is reduced such that a contact angle of pure water forthe surface of the substrate is smaller than 41.7°, and wherein thecontact angle of pure water for the processing film is larger than 52°and smaller than 61°.
 2. The substrate processing method according toclaim 1, wherein the peeling step includes a peeling liquid entry stepin which the peeling liquid enters between the surface of the substrateand the processing film.
 3. The substrate processing method according toclaim 1, wherein at least any one of Si, SiN, SiO₂, SiGe, Ge, SiCN, W,TiN, Co, Cu, Ru and amorphous carbon is exposed from the surface of thesubstrate.
 4. The substrate processing method according to claim 1,wherein the processing liquid contains a solvent and a solute, thesolute has a high solubility component and a low solubility componentwhich is lower in solubility in the peeling liquid than the highsolubility component, the processing film forming step includes a stepof forming the processing film having a high solubility solid formed bythe high solubility component and a low solubility solid formed by thelow solubility component, and in the peeling step, the high solubilitysolid is dissolved in the peeling liquid to peel the processing film ina state of holding the removal object from the surface of the substrate.5. The substrate processing method according to claim 1, wherein thehydrophilization step includes a step in which the hydrophilizing liquidis supplied to the surface of the substrate to hydrophilize the surfaceof the substrate.
 6. The substrate processing method according to claim5, wherein the hydrophilizing liquid is an oxidizing liquid or anorganic solvent.
 7. The substrate processing method according to claim5, wherein a surface layer of the substrate contains a TiN layer whichis exposed from the surface of the substrate, and the hydrophilizingliquid is an oxidizing liquid.